Liu entered the industry in 2000, when she was cast in the family sitcom Daughter-in-Law.
In 2003, Liu was cast in My Fair Princess III, playing the role of Musha. Following the series, Liu rose to fame in China. Her subsequent performance as A'zhu in Demi-Gods and Semi-Devils (2003) made her a household name.
In 2006, Liu starred in Madame White Snake and gained attention for her portrayal of the titular heroine.
Liu challenged her first antagonist role in Da Li Princess (2009) co-starring Ruby Lin. In 2012, she played Mazu in the television series of the same name. The drama gained high ratings during its run and won at the Outstanding Television Series award at the China TV Golden Eagle Award and Flying Apsaras Awards.
Liu's subsequent performance in To Elderly With Love (2013) garnered her the Best Actress award at the China TV Golden Eagle Award and the Best Performing Arts Award at the China Golden Eagle TV Arts Festival. The same year, she starred in Good Wife as a mother and housewife who struggles with the challenges of family-life. The family drama was a ratings hit and along with the discussion of Liu's own martial arrangements, became one of the most talked-about topics on Weibo. As a result, Liu gained a surge in popularity.
In 2015, she starred in acclaimed wuxia-historical series Nirvana in Fire. A wax figure based on her role "Ni Huang" was displayed in Beijing Madame Tussauds Wax Museum. The same year, she co-starred in The Legend of Mi Yue and won the Best Supporting Actress award at the Shanghai Television Festival.
In 2016, Liu headlined modern romance series, Ode to Joy. The drama garnered positive reviews and high ratings, and Liu was nominated as Best Actress at the Huading Awards and Shanghai Television Festival.
In 2017, Liu starred in historical drama The Advisors Alliance, portraying Zhang Chunhua, the wife of Sima Yi. The same year, she featured in the crime thriller Peace Breaker and action thriller The Foreigner.