Vince Vaughn – Real-life couple Vince Vaughn and Aniston co-starred in 2006's "The Break-Up," which is coincidentally what the couple did later that year.
Brad Pitt – Brad Pitt and Aniston, shown here at the premiere of "The Mexican" in 2001, began dating in 1998. The pair married in 2000 and announced their separation in 2005, the same year Pitt and Angelina Jolie's "Mr. and Mrs. Smith" hit theaters.
Tate Donovan – Tate Donovan and Aniston were engaged in the mid-'90s. Before the couple called it quits, he appeared on "Friends" as the boyfriend of Aniston's character, Rachel Greene.
Charlie Schlatter – Aniston and Charlie Schlatter appeared side by side on NBC's "Ferris Bueller" series in1990. The sitcom was short-lived, as was the couple's relationship.