Angelina Jolie attended the premiere of her new film, The Good Shephard, with Brad Pitt in New York on Monday, Dec. 11. Jolie also revealed the details of their relationship to Vogue in her first in-depth interview since settling down with Pitt after meeting him on the set of Mr. & Mrs. Smith — while he was still married to Jennifer Aniston!

“Brad was a huge surprise to me,” she said. “I, like most people, had a very distant impression of him from … the media. I think we were the last two people who were looking for a relationship. I certainly wasn’t,” she said. “I was quite content to be a single mom.”

Jolie says she and Pitt developed a friendship while shooting the film. “I think a few months in I realized, ‘God, I can’t wait to get to work,'” she said. “We just became kind of a pair.” The two remained “very, very good friends” until Brad announced his separation from Jennifer Aniston. “And then life developed in a way where we could be together, where it felt like something we would do, we should do.”

Jolie also dished “I did [once meet Aniston], but it was not a proper meeting. We’ve, like, passed each other and said ‘hi’ briefly, shook hands. But not a real sit-down-and-talk kind of meeting.” Asked if she would sit down and talk with Aniston, Jolie said, “That would be her decision, and I would welcome it.”

So, will Brangelina marry? “We both have been married before, so it’s not marriage that’s necessarily kept some people together. We are legally bound to our children, not to each other, and I think that’s the most important thing,” she said.