Billy Bob Thornton, Laura Dern, Angelina Jolie
Prior to adopting a million children with current husband Brad Pitt, you may remember that Angelina Jolie was first married to actor Billy Bob Thorton. In fact, Angelina even went as far as having the Bad Santa star's name tattooed on her arm and wearing a vial of his blood around her neck.
At the time, these two eccentric thespians seemed like kindred spirits. The only problem was that while they met, Billy Bob was already engaged. Thornton was set to marry Enlightened star Laura Dern, but broke it off as soon as he and Jolie hit it off. Commenting on the situation, Dern's quoted as saying, "I left our home to go and make a movie and while I was away, my boyfriend got married and I never heard from him again."