When: 1994-1997

Brad and Gwyneth were Hollywood's most beautiful couple. Hell, if there is one thing this list proves, it's that Brad + woman = Hollywood's most beautiful couple. But their sustained relationship and engagement made them extra-beautiful, and the mix-and-match hairdos were the icing on this cake of celebrity cuteness. So, of course it couldn't last.

Smash Probability: Are we to assume these two had premarital sex? Like, naked and everything? Gosh, it really is Sodom and Gomorrah out there in Hollywood.