61. Angelina Jolie & Billy Bob Thornton

Angelina Jolie and Billy Bob Thornton met, exchanged a few looks here and there, and started a relationship while filming the 1999 film Pushing Tin, where they played a husband and wife. Their instant connection continued to spark like electricity, with the two eloping in Las Vegas the following year.

Their relationship was full of wackiness and chaos. They swapped underwear, got matching name tattoos, and were not shy about public displays of affection. After just two years of tying the knot, Jolie and Thornton separated in August 2002. It was also the same year the Maleficent star adopted her first child, Maddox. The actress says they just grew apart and became different people. She became more politically active, while he was focused on his music career. Despite going their separate ways, both Jolie and Thornton still held each other in high regard and are friends to this day.