Prior to Brad Pitt and Jennifer Aniston’s split they really seemed like the perfect couple. Recommended VideosAs we all know, the couple’s marriage fell apart in 2005, conveniently around the same time rumors began circulating around Pitt having an affair with his Mr. and Mrs. Smith co-star, Angelina Jolie. What happened between Brad Pitt and Jennifer Aniston? Pitt had apparently denied sleeping with Jolie and Aniston had believed him. But Brad was saying, ‘This is not about another woman.’” But maybe giving Brad Pitt the benefit of the doubt was a mistake.