Brad Pitt and Angelina Jolie
Though he was married to Jennifer Aniston at the time, Pitt couldn’t take his eyes off of Jolie on the set of Mr. & Mrs. Smith in 2004. “I think we were the last two people who were looking for a relationship,” Jolie later told Vogue in 2006. It wasn’t until shooting nearly ended that Pitt and Jolie realized “it might mean something more than we’d earlier allowed ourselves to believe.” The pair were together for 10 years before marrying in August 2014. The Oscar-winning actress filed for divorce from the World War Z star in September 2016, with whom she shares kids Maddox, Pax, Zahara, Shiloh, Vivienne and Knox.
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