Need we even explain this couple's early run-in with heartbreak? When Brad and Angie first met, Brad was still married to Jennifer Aniston, and Angie was well-known for her H'wood bad-girl image. But their onscreen chemistry in Mr. & Mrs. Smith couldn't be tamed—the two paired up right after Brad left Jen. Fast-forward seven years later and Brad and Ange are still very much in love. With a world-traveling brood of six, they've officially cemented their status as Hollywood-couple royalty.