Jolie says that during filming, she and Pitt "were the last two people who were looking for a relationship. I certainly wasn't. I was quite content to be a single mom." Despite the fact that she wasn't seeking romance, Angelina easily connected with Brad. She explained, "Because of the film, we ended up being brought together to do all these crazy things, and I think we found this strange friendship and partnership that kind of just suddenly happened. I think a few months in I realized, 'God, I can't wait to get to work.'…Anything we had to do with each other, we just found a lot of joy in it together and a lot of real teamwork. We just became kind of a pair."

But even though Brad and Angelina connected as they acted together, they did not pursue a relationship at the time. Jolie says of Pitt's marriage to Jennifer Aniston at the time, "It was clear he was with his best friend, someone he loves and respects."

In fact, the pair didn't even consider a romance for some time. The actress says, "It took until, really, the end of the shoot for us, I think, to realize that it might mean something more than we'd earlier allowed ourselves to believe. And both knowing that the reality of that was a big thing, something that was going to take a lot of serious consideration…We spent a lot of time contemplating and thinking and talking about what we both wanted in life and realized that we wanted very, very similar things…We remained very, very good friends – with this realization – for a long time. And then life developed in a way where we could be together, where it felt like something we would do, we should do."

It was the couple's adopted child Maddox who solidified their commitment to one another when he "just out of the blue called [Brad] Dad," Jolie told Vogue. "It was amazing. We were playing with cars on the floor of a hotel room, and we both heard it and didn't say anything and just looked at each other. So that was probably the most defining moment, when he decided that we would all be a family."