| # | Name | Assumed office | Left office | President(s) served under |
| 1 | Philip Hall Coombs | March 23, 1961 | June 4, 1962 | John F. Kennedy |
| 2 | Lucius D. Battle | June 5, 1962 | August 20, 1964 | John F. Kennedy, Lyndon B. Johnson |
| 3 | Harry McPherson | August 23, 1964 | August 14, 1965 | Lyndon B. Johnson |
| 4 | Charles Frankel | September 15, 1965 | December 31, 1967 | Lyndon B. Johnson |
| 5 | Edward D. Re | February 28, 1968 | January 9, 1969 | Lyndon B. Johnson |
| 6 | John Richardson Jr. | July 15, 1969 | March 7, 1977 | Richard Nixon, Gerald Ford |
| 7 | Joseph D. Duffey | April 8, 1977 | March 21, 1978 | Jimmy Carter |
| 8 | Alice Stone Ilchman | March 22, 1978 | March 31, 1978 | Jimmy Carter |
| - | Position abolished | | | |
| 9 | William B. Bader | November 18, 1999 | January 20, 2001 | Bill Clinton |
| 10 | Patricia Harrison | October 2, 2001 | July 1, 2005 | George W. Bush |
| 11 | Dina Powell | July 11, 2005 | June 7, 2007 | George W. Bush |
| 12 | Goli Ameri | March 19, 2008 | January 20, 2009 | George W. Bush |
| 13 | Ann Stock | June 23, 2010 | August 16, 2013 | Barack Obama |
| 14 | Evan Ryan | September 26, 2013 | January 6, 2017 | Barack Obama |
| - | Mark Taplin | January 2017 | August 2017 | Donald Trump |
| - | Jennifer Zimdahl Galt | November 13, 2017 | March 29, 2018 | Donald Trump |
| 15 | Marie Royce | March 30, 2018 | January 20, 2021 | Donald Trump |
| - | Matthew Lussenhop | January 20, 2021 | November 22, 2021 | Joe Biden |
| 16 | Lee Satterfield | November 23, 2021 | January 20, 2025 | Joe Biden |
| - | Scott Weinhold | January 20, 2025 | February 4, 2025 | Donald Trump |
| - | Darren Beattie | February 4, 2025 | Incumbent | Donald Trump |