Brad Pitt and Angelina Jolie

Perhaps one of the most talked about on-screen-turned-off-screen couples is Brad Pitt and Angelina Jolie. Their romance reportedly began when the couple worked together on the sexy spy action-comedy Mr. and Mrs. Smith. Brad subsequently ended his marriage to five-year partner Jennifer Aniston telling Parade he was "trying to pretend the marriage was something that it wasn't." Of course, Brangelina is now in the midst of a tumultuous divorce.  

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