#10 Angelina Jolie and Brad Pitt
Mr. And Mrs. Smith Screenshot
Brad Pitt and Angelina Jolie first worked together on the action-comedy Mr. and Mrs. Smith. At the time of the movies production, Pitt was still married to Friends star Jennifer Aniston. After Pitt asked for a divorce and started dating Jolie, rumors swirled that their romance started on the movie set, a claim Pitt has long denied. Pitt and Jolie have now been together for 11 years and they have a brood of adopted children together.