When: 1998-2005

The prettiest boy in the world falls for an attractive sitcom star. After the fizzling of Paltrow-Pitt, surely Aniston-Pitt would last. And it did (kind of); the couple was married in 2000 and stayed that way for nearly five years. Then Hurricane Angelina busted Brad's levees on the set of Mr. & Mrs. Smith, and Jen's fairy-tale future was done for. 

Smash Probability: The rumor was that the couple split largely because Jen didn't want to make babies with Brad. Though we imagine they went through the motions quite a lot.