| John Foster Dulles | | Audience with Pope Pius XII. | October 23, 1955 |
| John Foster Dulles | | Attended funeral ceremonies for Pope Pius XII. | October 19, 1958 |
| William Pierce Rogers | | Accompanied President Nixon. | March 2, 1969 |
| William Pierce Rogers | | Audience with Pope Paul VI. | May 8, 1971 |
| William Pierce Rogers | | Audience with Pope Paul VI. | July 11, 1972 |
| Henry A. (Heinz Alfred) Kissinger | | Audience with Pope Paul VI. | July 6, 1974 |
| Henry A. (Heinz Alfred) Kissinger | | Accompanied President Ford. | June 3, 1975 |
| Cyrus Roberts Vance | | Audience with Pope John Paul II. | May 29, 1979 |
| Edmund Sixtus Muskie | | Accompanied President Carter. | June 21, 1980 |
| Alexander Meigs Haig | | Accompanied President Reagan. | June 7, 1982 |
| George Pratt Shultz | | Audience with Pope John Paul II. | March 29, 1986 |
| George Pratt Shultz | | Audience with Pope John Paul II. | April 2, 1988 |
| James Addison Baker | | Audience with Pope John Paul II. | May 27, 1989 |
| Warren Minor Christopher | | Accompanied President Clinton to Vatican City for meetings with senior church
officials. | June 2, 1994 |
| Madeleine Korbel Albright | | Discussed the Kosovo crisis with Pope John Paul II. | March 7, 1998 |
| Madeleine Korbel Albright | | Discussed the Kosovo crisis and the situation in Cuba with Vatican
officials. | March 24, 1998 |
| Madeleine Korbel Albright | | Met with Secretary for Relations with States Tauran. | July 28, 1999 |
| Madeleine Korbel Albright | | Briefed Foreign Minister Tauran on the Middle East peace process. | August 1, 2000 |
| Colin Luther Powell | | Met with Secretary of State Sodano. | May 28, 2002 |
| Colin Luther Powell | | Briefed Pope John Paul II on the Middle East Summit and relief efforts in
Iraq. | June 2, 2003 |
| Colin Luther Powell | | Accompanied President Bush. | June 4, 2004 |
| Condoleezza Rice | | Met with Cardinal Sodano. | February 8, 2005 |
| Condoleezza Rice | | Attended the funeral of Pope John Paul II. | April 6–9, 2005 |
| John Forbes Kerry | | Met with Secretary of State Pietro Parolin. | January 14, 2014 |
| John Forbes Kerry | | Accompanied President Obama. | March 25, 2014 |
| John Forbes Kerry | | Met with Secretary of State Cardinal Pietro Parolin. | December 2, 2016 |
| Rex W. Tillerson | | Accompanied President Trump. | May 24, 2017 |
| Michael R. Pompeo | | Audience with His Holiness Pope Francis and met with Secretary of State Cardinal
Pietro Parolin. | October 2–3, 2019 |
| Michael R. Pompeo | | Met with Secretary of State Cardinal Parolin and Secretary for Relations with
States Archbishop Gallagher. | September 30, 2020 |
| Antony Blinken | | Met with Pope Francis, Holy See Secretary of State Cardinal Pietro Parolin, and
Holy See Secretary for Relations with States Archbishop Paul Gallagher. | June 28, 2021 |
| Antony Blinken | | Joined the President and First Lady in an audience with His Holiness Pope
Francis. | October 29, 2021 |
