Angelina Jolie
Brad and Angelina played a married couple who doubled up as assasins in the 2003 action comedy 'Mr and Mrs Smith' and fell for each other on set.
The pair - known to fans around the world as 'Brangelina' - started to date after the 'Fight Club' actor had separated from Jennifer.
They had six children together and tied the knot in 2014, but filed for divorce just two years later. As of 2023, the pair remain legally single but divorce negotiations remain ongoing.