"I was really bummed that I didn't get Captain America," Sebastian Stan tells PEOPLE Now. "I remember getting the phone call and going, 'You were great, but it's not for you.' "
However, it all worked out for the best because he was offered the part of Bucky Barnes, Cap's best friend who appears to die in Captain America: The First Avenger only to return as the deadly HYDRA assassin Winter Soldier in Captain America: The Winter Solider.
"When they called me back again to tell me that there was this other role that I should be looking at, I was really excited because it wasn't over yet," he says.
Stan signed on to do nine movies with Marvel, which was "a little scary," he admits. "But, look, when you're working with someone like Marvel, I mean it's a blessing because the movies are different every time, so it's actually exciting to kind of come back to that," he says.
Three movies in, Stan has accepted that he ended up getting the right part.
"Playing an unstable, bipolar, multiple personality disorder person is definitely up my alley," he jokes.
Captain America: Civil War is in theaters now and also stars Robert Downey Jr., Scarlett Johansson, Anthony Mackie, Emily VanCamp, Don Cheadle, Chadwick Boseman, Paul Bettany, Elizabeth Olsen, Jeremy Renner, and Paul Rudd.