Brad Pitt & Jen Aniston
There was no bigger couple of the first half of the 21st century than Brad Pitt and Jennifer Aniston. The two began dating in 1998 and were married in 2000 in a private ceremony in Malibu, California. For 5 years they were the “it couple” in Hollywood.
Things began to fall apart for the couple and they announced their separation in early 2005. While divorce proceedings were taking place, Pitt struck up a relationship with his Mr. & Mrs. Smith co-star Angelina Jolie.