Brangelina first met when they filmed Mr. and Mrs. Smith together in 2004. At the time, Pitt was married to Jennifer Aniston. His on-screen chemistry with Jolie sparked cheating rumors, and clearly for good reason.
“I didn’t know much about exactly where Brad was in his personal life,” Jolie told Vogue in 2007. “I think we were the last two people who were looking for a relationship. I certainly wasn’t.”