Born on December 6, 1950, Smt. Rao joined the Indian Foreign Service in 1973. She has served in various world capitals, including Washington and Moscow. She has had extensive experience in relations between India and China, having served in the East Asia Division of the Ministry of External Affairs, New Delhi from 1984 to 1992, including as Joint Secretary (East Asia). Smt. Rao was a Fellow of the Centre for International Affairs (now the Weatherhead Centre) of Harvard University from 1992-93. She was Minister in the Indian Embassy in Washington from 1993-1995, in charge of Press Affairs.
From 1998-1999, she was Deputy Chief of Mission at the Indian Embassy in Moscow. In 1999-2000, she was Distinguished International Executive in Residence at the University of Maryland at College Park. From 2001 to 2002, she served as the first woman spokesperson of the Ministry of External Affairs. She was High Commissioner for India in Sri Lanka (2004-2006) and thereafter Ambassador of India to China (October 2006 – July 2009).
She is married to Shri Sudhakar Rao, a member of the Indian Administrative Service who is currently Chief Secretary, Government of Karnataka. They have two sons, Nikhilesh and Kartikeya.