Billy Bob Thornton
It's nearly impossible to forget the union between Angelina Jolie and Billy Bob Thornton, from the candid quotes about their sex life to the vials of each other's blood that they wore around their necks. The two met while filming 1999's Pushing Tin — and while Billy Bob was engaged to actress Laura Dern. He left Laura for Angelina (who was 20 years his junior), and they got married that year. In March 2002, the couple announced that they had adopted a baby boy, Maddox, from Cambodia, though it was later revealed that Angelina adopted him as a single parent. She and Billy Bob separated in June 2002 and were divorced in 2003, amid rumors that Maddox's adoption caused a rift in their relationship.