Married: Not yet Angelina Jolie and Brad Pitt met, and became close, while starring as warring spy spouses in the movie Mr. & Mrs. Smith in 2003. Although they have yet to become Mr. & Mrs. Pitt in real life, the duo (famously dubbed "Brangelina") has forged a family that includes six children who accompany their parents all across the globe. Jolie has denied that she and Pitt engaged in romance while he was still married to then-wife Jennifer Aniston, telling Vogue magazine in 2006 that, "He's somebody I admire based on the way he lives his life." And cementing their connection: the children. Jolie says she knew she and Pitt would be together when one day, out of the blue, her son Maddox called Pitt “Dad.” "It was amazing,” she said. “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 (Maddox) decided that we would all be a family."