| Portrait | Name | Took office | Left office | Appointer | Notes |
| 1 | | V. V. Giri | 1947 | 1951 | Lord Mountbatten | Later President of India |
| 2 | | K. P. Kesava Menon | 1951 | 1952 | Rajendra Prasad | |
| 3 | | Chandulal Chunilal Desai | 1953 | 1954 | Rajendra Prasad | Later Member of Parliament, Lok Sabha |
| 4 | | Birendra Narayan Chakraborty, | 1955 | 1956 | Rajendra Prasad | Later Governor of Haryana |
| 5 | | Y. D. Gundevia, | 1957 | 1960 | Rajendra Prasad | First term; later Foreign Secretary |
| 6 | | B. K. Kapur, | 1960 | 1964 | Rajendra Prasad | |
| 7 | | Bhim Sen Sachar | 1964 | 1967 | Sarvepalli Radhakrishnan | Formerly Chief Minister of Punjab ; Governor of Orissa and Andhra Pradesh |
| | Y. D. Gundevia, | 1967 | 1969 | Sarvepalli Radhakrishnan | Second term; formerly Foreign Secretary |
| 8 | | Yogendra Krishna Puri, | 1969 | 1972 | V. V. Giri | |
| 9 | | V. C. Coelho, | 1973 | 1975 | V. V. Giri | |
| 10 | | Gurbachan Singh, | 1975 | 1978 | Fakhruddin Ali Ahmed | |
| 11 | | Thomas Abraham, | 1978 | 1982 | Neelam Sanjiva Reddy | |
| 12 | | Surbir Jit Singh Chhatwal, | 1982 | 1985 | Zail Singh | |
| 13 | | Jyotindra Nath Dixit, | 1985 | 1989 | Zail Singh | Later Foreign Secretary ; and National Security Advisor |
| 14 | | Lakhan Lal Mehrotra, | 1989 | 1990 | Ramaswamy Venkataraman | |
| 15 | | Nagendra Nath Jha, | 1990 | 1993 | Ramaswamy Venkataraman | Later Lieutenant Governor of Andaman and Nicobar Islands ; and Lieutenant Governor of Pondicherry |
| 16 | | Nareshwar Dayal, | 1993 | 1997 | Shankar Dayal Sharma | |
| 17 | | Shivshankar Menon, | 1997 | 2000 | K. R. Narayanan | Later Foreign Secretary ; and National Security Advisor |
| 18 | | Gopalkrishna Gandhi, | 2000 | 2002 | K. R. Narayanan | Formerly Secretary to the President of India ; and later Governor of West Bengal |
| 19 | | Nirupem Sen, | 2002 | 2004 | K. R. Narayanan | - |
| 20 | | Nirupama Rao, | 2004 | 2006 | A. P. J. Abdul Kalam | Later Foreign Secretary |
| 21 | | Alok Prasad, | 2006 | 2009 | A. P. J. Abdul Kalam | Later Deputy National Security Advisor |
| 22 | | Ashok Kantha, | 2009 | 2013 | Pratibha Patil | |
| 23 | | Yashvardhan Kumar Sinha, | 2013 | 2016 | Pranab Mukherjee | Later Chief Information Commissioner |
| 24 | | Taranjit Singh Sandhu, | 2017 | 2020 | Pranab Mukherjee | |
| 25 | | Gopal Bagalay, | 2020 | 2023 | Ram Nath Kovind | |
| 26 | | Santosh Jha, | 2023 | Incumbent | Droupadi Murmu | |