Nirupama Rao, who has served as ambassador to China and spokesperson of the foreign ministry, takes charge as India's foreign secretary on Saturday.
Rao will be India's second woman foreign secretary after Chokila Iyer, who served briefly in the post in 2001.
A topper of the 1973 IFS batch, Rao became the first woman spokesperson of the external affairs ministry in 2001. In her 36-year career so far, she has served as ambassador in Peru, Sri Lanka and China and deputy chief of mission in Moscow.
Rao succeeds Shivshankar Menon, who ended his nearly three-year tenure as India's top diplomat on Friday.
Officers of the external affairs ministry held a farewell function for Menon Friday at South Block that was also attended by External Affairs Minister SM Krishna.
Menon is likely to join the Prime Minister's Office as prime minister's special envoy for the neighbourhood, reliable sources said.
Rao takes over as India's chief diplomat at a time when the neighbourhood is seething with problems and the government's Pakistan policy, after the Sharm el-Sheikh joint statement that delinks terror from composite dialogue and includes a reference to Balochistan, is being questioned by the opposition.