She broke into mainland China shortly after by starring in the TV drama Chinese Paladin, an adaptation of the fantasy RPG The Legend of Sword and Fairy.
Since then, she had been actively involved in both Chinese and Taiwanese productions, such as The Legend of Hero (2005), Fox Volant of the Snowy Mountain (2006), Fast Track Love (2006), The Great Revival (2007), and Yun Niang (2008).
In 2009, she signed with Huayi Brothers, and was cast as Zhao Min in the wuxia drama The Heaven Sword and Dragon Saber, an adaptation of the novel of the same title by Louis Cha.
An's known as the head of her group of celebrity friends, collectively known as An Corporation, including Joe Chen, Shone An, Esther Liu, Bianca Bai, Linda Liao and Kimi Hsia.
On April 21, 2023, Macau Primary Court’s first-instance verdict sentenced Chen to 14 years in prison on charges including illegal gambling, fraud, and money laundering.