In her career she served in several capacities including, Minister of Press, Information and Culture in Washington DC, Deputy Chief of Mission in Moscow, stints in the MEA as Joint Secretary, East Asia and External Publicity, the latter position making her the first woman spokesperson of the MEA, Chief of Personnel, Ambassador to Peru and China, and High Commissioner to Sri Lanka.

Her mother, Meempat Narayanikutty, was the first woman college graduate in her family, obtaining a BA Mathematics (Honors) degree from Madras University in 1947.

[11] Her interest in Tibetan affairs was consolidated with visits to the Tibet Autonomous Region, including the leading of a group of Indian pilgrims to the holy sites of Mt.

[citation needed] Rao was a Fellow at the Weatherhead Center for International Affairs at Harvard University in 1992–93 where she specialized on Asia-Pacific Security.

[citation needed] Following her time at Harvard, Rao served as Minister for Press, Information and Culture at the Indian Embassy in Washington D.C. from 1993 to 1995.

Following this posting, she returned to the United States as a Distinguished International Executive in Residence at the University of Maryland at College Park from 1999 to 2000.

In 2003, on the initiative of the then National Security Advisor and Principal Secretary to the Prime Minister, Brajesh Mishra, Rao became a member of the Special Representative's delegation for border talks with China.

[20] The operations by the Indian Navy to clear the Galle and Colombo harbors after the tsunami won special praise from the Sri Lankan government.

[21] The Indian government's relief efforts as first responder after the tsunami were widely praised in Sri Lanka for their promptness, efficacy and reach.

[24] The India-China Business Forum was also set up during this time, enabling a sharper focus on business-related activities concerning trade and investment between India and China.

[25] In 2009, at Rao's initiative, India sponsored a farmers’ training and information center in the far western province of Ningxia, a low income area.

[27] Rao's being summoned to the Chinese Ministry of Foreign Affairs at the early hour of 2 a.m. on 21 March 2008 during disturbances in Tibet was the subject of considerable focus and criticism in the Indian media.

[29] During her tenure Rao was active in handling India's relations with its neighbors and with the United States, Russia and Japan, besides multilateral issues including nuclear energy cooperation as well as climate change.

[34] Rao made special efforts to augment and intensify the activities of the Public Diplomacy Division of the Ministry of External Affairs increasing its outreach significantly.

[44] This period also saw the visit of Prime Minister Manmohan Singh to Washington in September 2013, two meetings of the India-U.S. Strategic Dialogue, and several ministerial-level interactions between the two countries.

Her tenure saw the purchase by the Indian Government (ending a quest that had lasted for close to four decades) of a property in downtown Washington D.C. to house the Center.

[46] Rao had consistently held that the fascination in the United States for Indian culture, the arts and letters of India, music and dance could be effectively leveraged to secure a deeper understanding and partnership.

[48] During the year, Rao was engaged in research on Sino-Indian diplomatic relations for what would eventually become her first work of historical non-fiction (The Fractured Himalaya: India Tibet China 1949-1962) and in writing on select foreign policy issues.

[51] In 2018, Rao was named the George Ball Adjunct Professor for the fall semester at the School of International and Public Affairs (SIPA) at Columbia University.

[55] Rao's first published work was a collection of her English language poems titled Rain Rising, which was released in India in 2004 by Rupa Publications.

[58] The Fractured Himalaya was met with critical acclaim upon its release, with many reviews considering it an authoritative work on the early diplomatic relations between India and the PRC.

Critics especially praised the book's emphasis on Tibet as an independent political and socio-cultural entity and its crucial role in the evolution of the India-China relationship prior to the Sino-Indian conflict of 1962.