April 4, 2014
- Chris Evans - Steve Rogers/Captain America, A World War II veteran who was enhanced to the peak of human physicality by an experimental serum, frozen in suspended animation, and is now struggling to adjust to the modern world, he reluctantly remained with S.H.I.E.L.D. because he has nowhere else to go, he is very uncomfortable with the way S.H.I.E.L.D., and in particular, Nick Fury, operates, in the end, Watches the death of Howard Stark, at the hands of Obediah Stane!
- Scarlett Johansson - Natasha Romanoff/Black Widow, A highly trained spy working for S.H.I.E.L.D., who partners with Rogers, while Clint is off for break time, near the end, it is revealed that she was proving to be an amazing athlete and scholar, while gaining distinction in the USSR as a ballerina, eventually she was arranged to marry Alexi Shostakov, a distinguished Soviety test pilot, however, a revised, retconned origin establishes her as being raised from very early childhood by the U.S.S.R.'s "Black Widow Ops" program, rather than solely by Ivan Petrovitch. Petrovitch had taken her to Department X, with other young female orphans, where she is trained in combat and espionage at the covert "Red Room" facility. There, she is bio-technologically and psycho-technologically enhanced—an accounting that provides a rationale for her unusually long and youthful lifespan. During that time, she had some training under Winter Soldier and the pair even had a short romance. Each Black Widow is deployed with false memories to help ensure her loyalty, Natasha eventually discovered this, in the end, It is revealed that she is the wife of Red Guardian!
- Sebastian Stan - Bucky Barnes/Winter Soldier, Steve Rogers' best friend, who is turned into a brainwashed assassin by Aleksander Lukin, he was lovers with Natasha, and he had caused the loss of Fury's eye, near the end, Steve was able to make Bucky remember who he was, in the end,
- Anthony Mackie - Sam Wilson/Falcon, A Harlem native with the ability to fly and speak telepathically with birds, he moved to Harlem and was a drug dealer, His plane crashed, and he was genetically altered, and he can fly, has telepathic powers, he teamed up with Captain America to find out about Winter Soldier, in the end,
- Cobie Smulders - Maria Hill, An agent with S.H.I.E.L.D. who works closely with Nick Fury, in the end,
- Frank Grillo - Brock Rumlow/Crossbones, an assassin who rivals against the Winter Soldier, which leads to an epic fight scene between them in the end, at Alaska, he later met up with Dell Rusk, who he apologizes to for his failure
- Georges St-Pierre - Georges Batroc, appears as a french mercenary and he speaks French, a martial arts expert of savate, Olympic lifting champion, he was seen at the beginning being stopped by Captain America and Black Widow on top of the Statue of Liberty
- Samuel L. Jackson - Nick Fury, the director of S.H.I.E.L.D., he lost eye to the Winter Soldier, in the end,
- Robert Redford - Aleksander Lukin/Alexander Pierce, a senior leader within S.H.I.E.L.D., revealed to be the main antagonist of the film, as he caused the Winter Soldier to be brainwashed and thawed out of ice, and the loss of Fury's eye, he ordered the near death of President Ellis by Winter Soldier, his country was attacked by Red Skull in the Second World War, in the end,
- Haylet Atwell - Peggy Carter, was mentioned having a heart attack at an older age, and Steve attended her funeral for her niece, Sharon, Peggy was seen in a flashback, dancing with Steve before Bucky's death
- Toby Jones - Arnim Zola, was seen in an android body after he had died in the 1940's, he created to transfer his mind into it, in the end,
- Maximiliano Hernández - Jasper Sitwell, was seen near the beginning telling Steve and Natasha that Fury needs them, and Natasha kicks him off, and Steve angrily grabs Sitwell by the collar telling him he reluctantly worked with S.H.I.E.L.D. because there was no place for him to go, in the end,
- Emily Vancamp - Sharon Carter/Agent 13 of S.H.I.E.L.D. and niece of Peggy Carter, had met Steve after he awaken from his coma in the prequel, in the end,
- Hugo Weaving - Dell Rusk, was at the end shaking hands with President Ellis as he was pronounced U.S. Secretary of Defense, then he went to his office all by himself by informing the Other of new plans to keep S.H.I.E.L.D. and the Avengers busy, Weaving uses the same tone as his character from Matrix, Agent Smith for Dell Rusk
- William Sadler - President Ellis, he was shocked of the Winter Soldier attacking the United States, in the end,
- Jeremy Renner - Clint Barton/Hawkeye, was seen at a post-credits scene finishing his leave of absense seeing the mountains, and he was introduced to by Fury by his new partner, Agent 19, who will go under the name, Mockingbird
- Cameron Diaz - Barbara Morse/Agent 19, was seen at a post-credits scene being introduced to Clint by Fury
- Alexis Denisof - The Other, was seen at the end talking with Rusk
- Dominic Cooper - Howard Stark, was seen on a video finishing his work and being confronted by Obadiah Stane, and being ???
- Jeff Bridges - Obadiah Stane, was seen on a video confronting Howard Stark and ???