Rather than go by individual movie, I'm just putting everyone together ('cos there are... a lot of movies)
MARVEL CINEMATIC UNIVERSE
Heroes
Avengers
Iron Man / Tony Stark -- Robert Downey Jr.
JARVIS -- Paul Bettany
FRIDAY -- Kerry Condon
Captain America / Steve Rogers -- Chris Evans
Black Widow / Natasha Romanoff -- Scarlett Johansson
Hawkeye / Clint Barton -- Jeremy Renner
Hulk / Bruce Banner -- Edward Norton, Mark Ruffalo, Lou Ferrigno (voice)
Thor -- Chris Hemsworth
Quicksilver / Pietro Maximoff -- Aaron Taylor-Johnson
Scarlet Witch / Wanda Maximoff -- Elizabeth Olsen
Vision -- Paul Bettany
Falcon / Sam Wilson -- Anthony Mackie
War Machine / Iron Patriot / James Rhodes -- Terrence Howard, Don Cheadle
Spider-Man / Peter Parker -- Tom Holland
Ant-Man / Scott Lang -- Paul Rudd
Black Panther / T'Challa -- Chadwick Boseman
Bucky / Winter Soldier / James Barnes -- Sebastian Stan
Captain Marvel / Carol Danvers -- Brie Larson
Doctor Strange / Stephen Strange -- Benedict Cumberbatch
Rescue / Pepper Potts -- Gwyneth Paltrow
Wasp / Hope van Dyne -- Evangeline Lilly
Guardians of the Galaxy
Star-Lord / Peter Quill -- Chris Pratt
Drax the Destroyer -- Dave Bautista
Gamora -- Zoe Saldana
Groot -- Vin Diesel
Rocket Raccoon -- Bradley Cooper
Nebula -- Karen Gillan
Mantis -- Pom Klementieff
Kraglin Obfonteri -- Sean Gunn
Cosmo --
Phyla-Vell -- Kai Zen
Ravagers
Yondu Udonta -- Michael Rooker
Stakar Ogord -- Sylvester Stallone
Aleta Ogord -- Michelle Yeoh
Mainframe -- Miley Cyrus, Tara Strong
Martinex -- Michael Rosenbaum
Eternals
Ajak -- Salma Hayek
Druig -- Barry Keoghan
Gilgamesh -- Don Lee
Ikaris -- Richard Madden
Kingo -- Kumail Nanjiani
Makkari -- Lauren Ridloff
Phastos -- Brian Tyree Henry
Sersi -- Gemma Chan
Sprite -- Lia McHugh
Starfox / Eros -- Harry Styles
Thena -- Angelina Jolie
Others
America Chavez -- Xochitl Gomez
Ant-Man / Hank Pym -- Michael Douglas
Blade / Eric Brooks -- Mahershala Ali
Korg -- Taika Waititi
"Lady Thor" / Jane Foster -- Natalie Portman
Shang-Chi / Xu Shang-Chi -- Simu Liu
Valkyrie / Brunnhilde -- Tessa Thompson
Wasp / Janet van Dyne -- Michelle Pfeiffer
Multiverse
Illuminati
Professor X / Charles Xavier -- Patrick Stewart
Black Bolt / Blackagar Boltagon -- Anson Mount
Captain Carter / Peggy Carter -- Hayley Atwell
Captain Marvel / Maria Rambeau -- Lashanna Lynch
Mr. Fantastic / Reed Richards -- John Krasinski
Spider-Men
Spider-Man / Peter Parker -- Tobey Maguire Spider-Man / Peter Parker -- Andrew Garfield
Villains
Black Order
Thanos --Damion Poitier, Josh Brolin
Corvus Glaive -- Michael James Law
Cull Obsidian -- Terry Notary
Ebony Maw --Tom Vaughan-Lawlor
Proxima Midnight -- Carrie Coon
Hydra
Red Skull / Johann Schmidt -- Hugo Weaving, Ross Marquand
Arnim Zola -- Toby Jones
Baron Wolfgang von Strucker --Thomas Kretschmann
Crossbones / Brock Rumlow -- Frank Grillo
Heinz Kruger -- Richard Armitage
AIM
Aldrich Killian -- Guy Pearce
Ellen Brandt --Stephanie Szostak
Asgardians
Loki -- Tom Hiddleston
Hela -- Cate Blanchett
Hammer Industries
Justin Hammer -- Sam Rockwell
Whiplash / Ivan Vanko -- Mickey Rourke
Kree Empire
Ronan the Accuser -- Lee Pace
Korath the Pursuer -- Djimon Hounsou
Ravagers
Taserface -- Chris Sullivan
Brahl -- Stephen Blackehart
Ten Rings
Mandarin / Xu Wenwu -- Tony Leung
Raza -- Faran Tahir
Death-Dealer / Li Ching-Lin -- Andy Le
Razor Fist -- Florian Munteanu
Zealots
Dormammu -- Benedict Cumberbatch
Kaecilius -- Mads Mikkelsen
Bestman Salvage
Vulture / Adrian Toomes -- Michael Keaton
Shocker / Jackson Brice -- Logan Marshall-Green
Shocker / Herman Schultz -- Bokeem Woodbine
Tinkerer / Phineas Mason -- Michael Chernus
Others
Abomination / Emil Blonsky -- Tim Roth
Baron Mordo / Karl Mordo --Chiwetel Ejiofor
Ego -- Kurt Russell
Erik Killmonger / Erik Stevens / N'Jadaka -- Michael B. Jordan
Ghost / Ava Starr -- Hannah John-Kamen
Iron Monger / Obadiah Stane -- Jeff Bridges
Kurse / Algrim --Adewale Akinnuoye-Agbaje
Laufey -- Colm Feore
Malekith -- Christopher Eccleston
Mandarin / Trevor Slattery -- Ben Kingsley
Mysterio / Quentin Beck -- Jake Gyllenhaal
The Other -- Alexis Denisof
Surtur -- Clancy Brown
Ultron -- James Spader
Ulysses Klaue -- Andy Serkis
Yellowjacket / MODOK / Darren Cross -- Corey Stoll
Multiverse
Spider-Man villains
Green Goblin / Norman Osborn -- Willem Dafoe
Doctor Octopus / Otto Octavius -- Alfred Molina
Electro / Max Dillon -- Jamie Foxx
Lizard / Curt Connors -- Rhys Ifans
Sandman / Flint Marko -- Thomas Haden Church
Venom / Eddie Brock -- Tom Hardy
Other humans
S.H.I.E.L.D.
Nick Fury -- Samuel L. Jackson
Peggy Carter -- Hayley Atwell
Sharon Carter -- Emily VanCamp
Phil Coulson -- Clark Gregg
Maria Hill -- Cobie Smulders
Jasper Sitwell --Maximiliano Hernandez
Stark Industries
Howard Stark -- John Slattery, Dominic Cooper
Happy Hogan -- Jon Favreau
William Ginter Riva -- Peter Billingsley
Anton Vanko -- Yevgeni Lazarev
Culver University
Betty Ross -- Liv Tyler
Darcy Lewis -- Kat Dennings
Leonard Samson -- Ty Burrell
Erik Selvig -- Stellan Skarsgard
Jim Wilson -- P.J. Kerr
Howling Commandos
Dum Dum Dugan / Timothy Dugan -- Neal McDonough
Jacques Dernier -- Bruno Ricci
James Montgomery Falsworth -- JJ Feild
Gabe Jones -- Derek Luke
Jim Morita -- Kenneth Choi
Masters of the Mystic Arts
Wong -- Benedict Wong
Ancient One -- Tilda Swinton
Midtown School
Michelle "MJ" Jones -- Zendaya
Sally Avril -- Isabella Amara
Betty Brant --Angourie Rice
Ned Leeds -- Jacob Batalon
Roger Harrington -- Martin Starr
Flash Thompson -- Tony Revolori
United States government
Thaddeus "Thunderbolt" Ross -- William Hurt
Senator Stern -- Garry Shandling
United States military
Joe Greller -- Peter Mensah
Gilmore Hodge -- Lex Shrapnel
Chester Phillips -- Tommy Lee Jones
Kathleen Sparr -- Christina Cabot
Wakanda
T'Chaka -- John Kani
Ramonda -- Angela Bassett
Shuri -- Letitia Wright
Nakia -- Lupita Nyong'o
Okoye -- Danai Gurira
Zuri -- Forest Whitaker
WHH World News
Christine Everhart -- Leslie Bibb
Chess Roberts -- Olivia Munn
Other
Matthew Ellis -- William Sadler
Abraham Erskine -- Stanley Tucci
Maya Hansen -- Rebecca Hall
J. Jonah Jameson -- J.K. Simmons
Harley Keener -- Ty Simpkins
Cassie Lang -- Abby Ryder Forston,Emma Fuhrmann
Luis -- Michael Pena
Christine Palmer -- Rachel McAdams
May Parker -- Marisa Tomei
Meredith Quill -- Laura Haddock
Jason Quill -- Gregg Henry
Samuel Sterns -- Tim Blake Nelson
Ho Yinsen -- Shaun Toub
Others
Asgardians Odin -- Anthony Hopkins Frigga -- Rene Russo Fandral -- Josh Dallas, Zachary Levi Heimdall -- Idris Elba Hogun -- Tadanobu Asano Sif -- Jaimie Alexander Volstagg -- Ray Stevenson Celestials Arishem -- David Kaye Other The Collector / Taneleer Tivan -- Benicio del Toro
PHASE TWO
Thor: The Dark World (November 2013) [Alan Taylor]
Tony Curran -- Bor
Jonathan Howard -- Ian Boothby
Alice Krige -- Eir
Ophelia Lovibond -- Carina
Clive Russell -- Tyr
Captain America: The Winter Soldier (April 2014) [Anthony & Joe Russo]
Henry Goodman -- Dr. List
Callan Mulvey -- Jack Rollins
Robert Redford -- Alexander Pierce
Garry Shandling -- Senator Stern
Georges St-Pierre -- Georges Batroc
Guardians of the Galaxy (August 2014) [James Gunn]
Glenn Close -- Nova Prime
Marama Corlett -- Pit Biss
Christopher Fairbank -- The Broker
Seth Green -- Howard the Duck
Melia Kreiling -- Bereet
Ophelia Lovibond -- Carina
Tom Proctor -- Horuz
John C. Reilly -- Rhomman Dey
Alexis Rodney -- Moloka Dar
Peter Serafinowicz -- Garthan Saal
Avengers: Age of Ultron (May 2015) [Joss Whedon]
Linda Cardellini -- Laura Burton
Julie Delpy -- Madame B.
Henry Goodman -- Dr. List
Claudia Kim -- Helen Cho
Ant-Man (July 2015) [Peyton Reed]
Bobby Cannavale -- Jim Paxton
Martin Donovan -- Mitchell Carson
Judy Greer -- Maggie
PHASE THREE
Captain America: Civil War (May 2016) [Anthony & Joe Russo]
Daniel Bruhl -- Helmut Zemo
Hope Davis -- Maria Stark
Gene Farber -- Vasily Karpov
Martin Freeman -- Everett K. Ross
Florence Kasumba -- Ayo
Joe Russo -- Theo Broussard
Alfre Woodard -- Miriam Sharpe
Doctor Strange (November 2016) [Scott Derrickson]
Scott Adkins -- Lucian
Benjamin Bratt -- Jonathan Pangborn
Mark Anthony Brighton -- Daniel Drumm
Linda Louise Duan -- Tina Minoru
Amy Landecker -- Bruner [deleted scenes]
Michael Stuhlbarg -- Nicodemus West
Topo Wresniwiro -- Hamir
Guardians of the Galaxy Vol. 2 (May 2017) [James Gunn]
Steve Agee -- Gef
Elizabeth Debicki -- Ayesha
Mike Escamilla -- Scrote
Tommy Flanagan -- Tullk
Joe Fria -- Oblo
Seth Green -- Howard the Duck
Evan Jones -- Retch
Ving Rhames -- Charlie-27
Terence Rosemore -- Narblik
Jimmy Urine -- Half-Nut
Rob Zombie -- Ravager
Spider-Man: Homecoming (July 2017) [Jon Watts]
Tunde Adebimpe -- Mr. Cobbwell
Abraham Attah -- Abe Brown
Michael Barbieri -- Charles Murphy
Garcelle Beauvais -- Doris Toomes
Christopher Berry -- Randy Vale
Hannibal Buress -- Coach Wilson
Kenneth Choi -- Principal Morita
Jennifer Connelly -- Karen
Tyne Daly -- Anne Marie Hoag
Ethan Dizon -- Tiny
Tiffany Espensen -- Cindy Moon
Donald Glover -- Aaron Davis
Laura Harrier -- Liz Allan
Jorge Lendeborg Jr. -- Jason Ionello
Selenis Leyva -- Ms. Warren
Hemky Madera -- Mr. Delmar
Michael Mando -- Mac Gargan
John Penick -- Mr. Hapgood
Marin Starr -- Roger Harrington
J.J. Totah -- Seymour O'Reilly
Thor: Ragnarok (November 2017) [Taika Waititi]
Jeff Goldblum -- Grandmaster
Rachel House -- Topaz
Karl Urban -- Skurge
Black Panther (February 2018) [Ryan Coogler]
Sterling K. Brown -- N'Jobu
Seth Carr -- Erik Stevens (Young)
Winston Duke -- M'Baku
Martin Freeman -- Everett K. Ross
Daniel Kaluuya -- W'Kabi
Florence Kasumba -- Ayo
Trevor Noah -- Griot
Sydelle Noel -- Xoliswa
Avengers: Infinity War (April 2018) [Anthony & Joe Russo]
Peter Dinklage -- Eitri
Ethan Dizon -- Tiny
Winston Duke -- M'Baku
Tiffany Espensen -- Cindy Moon
Florence Kasumba -- Ayo
Ant-Man and the Wasp (July 2018) [Peyton Reed]
Rob Archer -- Knox
Bobby Cannavale -- Jim Paxton
Michael Cerveris -- Elihas Starr
Laurence Fishburner -- Bill Foster
Walton Goggins -- Sonny Burch
Judy Greer -- Maggie
Tim Heidecker -- Daniel Gooobler
Randall Park -- Jimmy Woo
Riann Steele -- Catherine Starr
Captain Marvel (March 2019) [Anna Boden, Ryan Fleck]
Akira Akbar -- Monica Rambeau (11-year-old)
Azari Akbar -- Monica Rambeau (5 years old)
Annette Bening -- Mar-Vell / Wendy Lawson, Supreme Intelligence
Sharon Blynn -- Soren
Gemma Chan -- Minn-Erva
Colin Ford -- Steve Danvers
Robert Kazinsky -- The Don
Jude Law -- Yon-Rogg
Stan Lee -- Himself
Ben Mendelsohn -- Talos / Keller
Kenneth Mitchell -- Mr. Danvers
Chuku Modu -- Soh-Larr
Vik Sahay -- Torfan
Algenis Perez Soto -- Att-Lass
Rune Temte -- Bron-Char
Avengers: Endgame (April 2019) [Anthony & Joe Russo]
Linda Cardenlli -- Laura Barton
James D'Arcy -- Edwin Jarvis
Winston Duke -- M'Baku
Katherine Langford -- Older Morgan Stark [deleted scene]
Callan Mulvey -- Jack Rollins
Alexandra Rabe -- Morgan Stark
Robert Redford -- Alexander Pierce
Ava Russo -- Lila Barton
Hiroyuki Sanada -- Akihiko
Spider-Man: Far From Home (July 2019) [Jon Watts]
Numan Acar -- Dimitri
Peter Billingsley -- William Ginter Riva
Sharon Blynn -- Soren
Remy Hii -- Brad Davis
Dawn Michelle King -- E.D.I.T.H.
Ben Mendelsohn -- Talos
J.B. Smoove -- Julius Dell
PHASE FOUR
Black Widow (July 2021, scheduled) [Cate Shortland]
O-T fa*gbenle -- Rick Mason
David Harbour -- Red Guardian / Alexei Shostakov
Florence Pugh -- Black Widow / Yelena Belova
Rachel Weisz -- Black Widow / Melina Vostokoff
Ray Winstone -- Dreykov
Eternals (November 2021, scheduled) [Chloe Zhao]
Kit Harington -- Dane Whitman
Spider-Man: No Way Home (December 2021, scheduled) [Jon Watts]
Hannibal Buress -- Coach Wilson
Thor: Love and Thunder (May 2022, scheduled) [Taika Waititi]
Christian Bale -- Gorr the God Butcher
