Immediately following her admittance into Beijing Film Academy, Liu received offers to star in various television drama serials. Her first role on television was in The Story of a Noble Family. Shortly after, she was chosen to play the role of Wang Yuyan in Demi-Gods and Semi-Devils, an adaptation of Louis Cha's wuxia novel of the same title. Initially, Liu Tao was selected for the role of Wang Yuyan but it went to Liu Yifei eventually and Liu Tao was cast as A'zhu instead.
In 2005, Liu starred as Zhao Ling'er in Chinese Paladin, an adaptation of the RPG The Legend of Sword and Fairy. The following year, she starred in another TV series adaptation of Louis Cha's wuxia novel The Return of the Condor Heroes. After intense speculation on who would play XiaolongnÃ¼, the role was finally offered to her. She was backed by Cha, who felt that she had all the necessary qualities to play the role of the young and innocent female protagonist. Although the drama serials she has acted in were well-received, the films she starred in did poorly in terms of box office earnings with the exception of The Forbidden Kingdom.
Liu appeared in Jimmy Lin's music video of the song "I Am Still Waiting For You" (我还在等你) from his 2006 album Can't Stop Me (挡不住我). She has also previously co-starred with him in Demi-Gods and Semi-Devils and The Love Winner. In conjunction with her acting career, Liu obtained a recording contract with Sony Music Entertainment Japan in August 2005. She has started studying singing and dancing in Japan since then. She released her first single "Mayonaka no Door" with Sony Music on July 19, 2006. Her song "Mayonaka no Doa" as recorded by Sony Music appeared on television as one of the ending themes to Demashita! Powerpuff Girls Z.
In 2008, she co-starred with martial arts film superstars Jet Li and Jackie Chan in The Forbidden Kingdom, in which she played Golden Sparrow, an orphan seeking revenge against her parents' killer. In 2010, she starred in Love In Disguise with Leehom Wang.