She became known for her role in the television series Ally McBeal (1998–2002) as the vicious and ill-mannered Ling Woo, and has also appeared in several notable film roles, including Charlie's Angels, Chicago, Kill Bill, and Kung Fu Panda.
Liu has guest starred as lawyer Grace Chin on Ugly Betty in the episodes "Derailed" and "Icing on the Cake". In a 2001 episode of Sex and the City entitled "Coulda, Woulda, Shoulda" she guest starred as herself, playing a new client of character Samantha Jones, who does public relations. She starred in the Sex and the City inspired TV show, Cashmere Mafia on ABC. In 2007, Empire magazine named her among the "100 Sexiest Movie Stars".
In 2008, after pitching an interest in being part of the hit new show Dirty Sexy Money, the producers immediately created a role for her as a series regular. She played the role of Nola Lyons, a powerful attorney that faced Nick George (played by Peter Krause). She is the voice for Silvermist in Disney Fairies franchise. She also appeared in Kung Fu Panda, an animated film in which she voiced Viper.
On March 2, 2010, Liu made her Broadway debut in the Tony Award-winning play God of Carnage playing Annette as part of the second replacement cast along side Jeff Daniels, Janet McTeer and Dylan Baker.