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Munn co-starred as Cindy in the short-lived ABC sitcom Carpoolers that ran from October 2, 2007 to March 4, 2008.
Munn's further auditions led to small roles in Hollywood productions; most notably in the drama White Oleander opposite Alison Lohman, Michelle Pfeiffer, Robin Wright-Penn and Renee Zellweger, based on the Janet Fitch novel of the same name, and in Cameron Crowe's romantic tragicomedy Elizabethtown opposite Orlando Bloom and Kirsten Dunst.
Munn's biggest break came in September 2003 when she won a co-starring role, opposite Amanda Bynes and Jennie Garth, on The WB sitcom What I Like About You in the second season as Tina Haven, Holly Tyler's new best friend.
Munn graduated from AC Flora High School and The College of Charleston.
From there, she moved to New York, where she won a role in the Off-Broadway classic, The Fantasticks.