Celebrity Couples and How They First Met: Love Story Beginnings

Brad Pitt and Angelina Jolie

Hollywood's ultimate power couple first met on the set of Mr. and Mrs. Smith back in 2004. At the time of their first encounter, Pitt was still married to Jennifer Aniston. "I didn't know much about exactly where Brad was in his personal life," Jolie said in Vogue's January 2007 issue. "I think we were the last two people who were looking for a relationship. I certainly wasn't."

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