1. Facing Off
It all started when Brad and Angelina were cast in the action flick Mr. & Mrs. Smith in 2005, and those who saw it can attest that the chemistry was palpable. Despite mixed reviews from critics, it earned a bundle and became one of the biggest hits of the year. Angelina said later of their children watching the film, "Not a lot of people get to see a movie where their parents fell in love."