Brad Pitt and Angelina Jolie

Perhaps one of the most talked about onscreen-turned-offscreen 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.