Angelina Jolie and Brad Pitt have been a celebrity couple in the news ever since they started dating after starring in Mr. & Mrs. Smith. But sadly. Here’s the Complete History of Angelina Jolie and Brad Pitt’s Relationship. On Tuesday, Angelina Jolie filed for divorce from Brad Pitt, her husband of two years and partner of nearly 12 years. Summer Brad Pitt and Angelina Jolie start filming Mr. and Mrs. Smith, a steamy. Angelina Jolie has reportedly filed for divorce from Brad Pitt; here's a look back at their year relationship.