"I just have to keep remembering that I don't know him on this show, because it's so comfortable and so nice to be with him," said Courteney, 49, who married Matthew's character on Friends.
In the episode, Matthew, 44, guest stars as Sam, a handsome man who gets into a car accident with Courteney's character Jules, who has let her car insurance lapse. Having lost her wedding ring in the fender bender, Sam asks Jules on a date and she accepts.
While fans are sure to go crazy for Matthew and Courteney sharing the screen again, of course the question on everyone's mind is will there ever be an official Friends reunion.
"There's such an overwhelming desire for it that maybe at some point there will be," said Matthew.
This special episode of Cougar Town airs Tuesday, January 14 on TBS.