Also starring is James D'Arcy as Edwin Jarvis, butler to Howard Stark who joins Carter for her missions, developing a strong platonic relationship with her.
The pair are joined by series regulars Chad Michael Murray as Jack Thompson and Enver Gjokaj as Daniel Sousa, as well as Shea Whigham as Roger Dooley for the first season.
Margaret Elizabeth "Peggy" Carter (portrayed by Hayley Atwell) is an officer with the Strategic Scientific Reserve (SSR) who worked with Captain America during World War II, falling in love with him before he seemingly sacrificed himself to stop the Nazi-division Hydra.
Approached by Howard Stark, whom she had also worked with during the war, to help clear his name after being framed for selling weapons to the USSR, Carter agrees to go behind the backs of her superiors.
[3] Atwell said it was "thrilling" to explore "the backdrop of this male-dominated world, where women are still in the workforce, unspoken for and struggling to find a place outside the home" and how it affects Carter, who must deal with this along with the missions she receives.
[7] Speaking about the influence that the apparent death of Steve Rogers has on Carter, Atwell explained that "It's only been a year and she's grieving him and I think what keeps her going is he was the greatest person she ever knew ... she's also determined to make sure that his work wasn't in vain.
[9] For the second season, executive producer Michele Fazekas explained that after Carter "put a lot of things emotionally to bed", such as letting go of Captain America, she is now "more open to looking at her life and figuring out, does she want a relationship?"
[12] Edwin Jarvis (portrayed by James D'Arcy) was charged with treason during the war after he forged the signature of his superior officer in an attempt to save the woman that would become his wife, Ana.
[13] The official tie-in comic Iron Man 2: Public Identity explained that a more comic-accurate version of the character did exist in the MCU, with the butler Jarvis serving as a mentor to a young Tony and eventually inspiring his A.I.
"[16] D'Arcy was initially nervous about portraying Jarvis's comedic side, given his history of "predominantly play[ing] psychopaths",[17] and did not study Paul Bettany's performance as J.A.R.V.I.S.
[10] Executive producer Tara Butters compared the relationship to that of Fox Mulder and Dana Scully in the early seasons of The X-Files, where "you really believed they cared about each other but it wasn't sexual.
[21] Jack Thompson (portrayed by Chad Michael Murray) is a war veteran and agent with the SSR who accidentally killed surrendering enemy soldiers, but hid the mistake, instead being praised as a hero.
[22] He noted that, unlike his character on One Tree Hill, Thompson does not serve as the "moral compass" of the series, which meant that he would not be "confined to a box" and would instead be allowed to "really play things up and do what's unexpected.
"[24] Daniel Sousa (portrayed by Enver Gjokaj) is a war veteran and agent with the SSR who experiences prejudice due to his crippled leg, for which he uses a crutch to support himself.
"[30] The costumes for the SSR agents in the series are meant to be distinctive to help explain their characters:[5] Sousa wears "sweater vests under his sport coats and pleated pants".
He continued, "I love dipping into ... some of that material of Howard Hughes, which I'm sure he's kind of been likened to", and described his biggest challenge in playing the character as "keeping it very realistic, but at the same time, tongue-in-cheek as well", and not making Stark "too broad".
She respects him hugely, but is also not afraid to comment on his lifestyle choices and how disgustingly misogynistic she finds him ... he does use women as a form of escapism for him and his Dionysian ways, but when it comes to Peggy, he doesn't see her as big boobs and red lips.
[49] Fay and the Griffith Hotel were introduced as a way to have more female characters in the series, as "We were troublingly dominated by men given that [Carter] was the only woman working in the SSR".
"[50] Dorothy "Dottie" Underwood (portrayed by Bridget Regan) is a Russian sleeper agent disguised as a small-town girl from Iowa who moves next door to Carter.
Underwood was created to give Carter a "strong female antagonist", and Butters noted that "we said, wouldn't it be great to have one of those people who is living right there with her be actually a bad guy?
[53] Regan did not know the character was a Black Widow when auditioning, but quickly learned after being cast, as the showrunners wanted her to change her then current red hair, in order to avoid being "a tip to the audience, because of Natasha [Romanoff].
[31] Johann Fennhoff (portrayed by Ralph Brown)[57] is a Russian hypnotist working for Leviathan, whose brother died from the effects of Stark's chemical weapon Midnight Oil.
[59] Whitney Frost (portrayed by Wynn Everett) is the stage name of Agnes Cully,[60] an actress and scientific genius forced to hide behind her husband, senatorial candidate Calvin Chadwick, due to the sexism of the age.
[69] Austin noted that this experience causes both fear and curiosity in Wilkes, and forces his role in the series to be more cerebral rather than action-focused as he is relegated to explaining science and planning until he regains his tangibility.
[62] He compared his relationship to Frost to that of Bill and Hillary Clinton, calling them "a power couple" and adding, "I think that Chadwick was probably attracted to her because of her beauty, [but she's] also a very smart woman, very successful, also probably a Type A.
"[71] D'Arcy later revealed that Verbeek had improvised this on their first day on set, after having "just flown in", calling it "brilliantly courageous ... to do it to an actor you don't know" and "so perfectly what they were hoping that Ana would be like.
"[74] Aloysius Samberly (portrayed by Matt Braunger) is an SSR lab tech who eventually goes out into the field with Carter, Sousa, Jarvis and Roberts to help them retrieve old atomic bombs at Roxxon Oil.
In October 2015, Smith was cast in the "major recurring role" of Masters for the second season, having previously worked with Butters and Fazekas on their television series Resurrection.
[76] The character was intended to be killed off at the end of the season, and a version of that was filmed, but the writers ultimately decided to leave Masters' fate "ambiguous" as they enjoyed working with Smith, with Fazekas saying, "The nice thing about that is we could go both ways on it.
"[77] Joseph Manfredi (portrayed by Ken Marino) is the leader of the Maggia crime syndicate branch in Los Angeles who aids Frost, having previously dated her.