Munn was born and raised in Columbia, South Carolina. Her father was Russell Munn, a political lobbyist. Munn graduated from AC Flora High School and The College of Charleston. She moved to New York, where she won a role in the Off-Broadway classic The Fantasticks.
Munn followed her stage roles with small roles in White Oleander, the film adaptation of the Janet Fitch novel of the same name, opposite Alison Lohman, Michelle Pfeiffer, Robin Wright-Penn and Renée Zellweger, and in Cameron Crowe's romantic tragicomedy Elizabethtown opposite Orlando Bloom and Kirsten Dunst.
In September 2003, Munn won a co-starring role opposite Amanda Bynes and Jennie Garth in the second season of The WB sitcom What I Like About You as Tina Haven, Holly Tyler's new best friend. Although their characters were the same age, Munn is eleven-and-a-half years older than her co-star Bynes. Munn remained on the show until the show ended with the fourth season on April 24, 2006. Munn also had a recurring role as Caroline, Fez's borderline stalker girlfriend on the Fox sitcom That '70s Show.

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