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Brad Pitt and Angelina Jolie
It's almost hard to imagine that the word Brangelina didn't always exist. Although they are without a doubt the super-couple of Hollywood's modern age, their courtship began with controversy. The duo met while filming the married-spies action film, Mr. and Mrs. Smith in 2004, and reports that their on-screen chemistry had translated to an off-screen romance — even though Pitt was still married to Jennifer Aniston — were on the cover of every tabloid. Though both denied the reports, the couple was photographed together in Kenya one month after Aniston filed for divorce. They have not married, but have six children, three of whom they adopted.