This is just all around a sticky situation, and as some call it – the split of the century. One of the most famous couples of all time, Pitt and Aniston wed in Malibu in 2000. This couple looked perfect. The love didn't last too long for the pair as Pitt was then cast in a role that would change his life for ever. Mr. and Mrs. Smith was originally to be played by Pitt and Nicole Kidman, but Pitt pulled out due to a lack of chemistry between the two. Que, Jolie. After denying the love for months, Pitt finally confessed his love for Jolie, Aniston then filed for divorce in March 2005.