Modeling
While studying in Sophia College, Rao auditioned for an advertisement for Fairever Face Cream. Her appearance in Cadbury’s Perk Karwa Chaut ad and the Bru Coffee advertisement helped her receive offers from film directors in Bollywood. As she wanted to complete her education, she refused them. After earning a degree in psychology, she began her profession as an actress, working in numerous films.
Acting
Rao made her acting debut with Ab Ke Baras (2002), and followed that with her 2003 film, Ishq Vishk, in which she portrayed Payal. In 2004 her films Masti and Main Hoon Na, Deewaar (2004) were released. Vaah! Life Ho To Aisi (2005), Shikhar (2005), and Pyare Mohan (2006) followed. She starred in Sooraj R. Barjatya's Vivah (2006) opposite Shahid Kapoor. Her performance earned her a Dadasaheb Phalke Academy Award.