Munn's further auditions led to small roles in Hollywood productions; most notably in White Oleander alongside Michelle Pfeiffer and in Elizabethtown, directed by Cameron Crowe.

Her biggest break came in 2002 when she got a co-starring role, opposite Amanda Bynes and Jennie Garth, on the sitcom What I Like About You. She also has a level of notoriety for a recurring role as Caroline, Fez's Read more...

Munn lives in Los Angeles with her pet terrier, Buster Keaton. On November 17, 2007, she married childhood friend and actor Scott Holroyd at the French Huguenot Church in Charleston, South Carolina.

She lends her name and support to the non-profit political organization, Rock the Vote, where she is actively involved in encouraging young people to register to vote.