| President | Secretary of State |
| George Washington | Thomas Jefferson |
| 1789–1797 | March 1790–December 1793 |
| Edmund Randolph | |
| January 1794–August 1795 | |
| Timothy Pickering | |
| December 1795–March 1797 | |
| John Adams | Timothy Pickering |
| 1797–1801 | March 1797–May 1800 |
| John Marshall | |
| June 1800–February 1801 | |
| Thomas Jefferson | James Madison |
| 1801–1809 | May 1801–March 1809 |
| James Madison | Robert Smith |
| 1809–1817 | March 1809–April 1811 |
| James Monroe | |
| April 1811–September 1814 | |
| February 1815–March 1817 | |
| James Monroe | John Quincy Adams |
| 1817–1825 | September 1817–March 1825 |
| John Quincy Adams | Henry Clay |
| 1825–1829 | March 1825–March 1829 |
| Andrew Jackson | Martin Van Buren |
| 1829–1837 | March 1829–March 1831 |
| Edward Livingston | |
| May 1831–May 1833 | |
| Louis McLane | |
| May 1831–May 1833 | |
| John Forsyth | |
| July 1834–March 1837 | |
| Martin Van Buren | John Forsyth |
| 1837–1841 | March 1837–March 1841 |
| William Henry Harrison | Daniel Webster |
| 1841 | March 1841 |
| John Tyler | Daniel Webster |
| 1841–1845 | April 1841–May 1843 |
| Abel P. Upshur | |
| July 1843–February 1844 | |
| John C. Calhoun | |
| April 1844–March 1845 | |
| James Polk | James Buchanan |
| 1845–1849 | March 1845–March 1849 |
| Zachary Taylor | John M. Clayton |
| 1849–1850 | March 1849–July 1850 |
| Millard Fillmore | Daniel Webster |
| 1850–1853 | July 1850–October 1852 |
| Edward Everett | |
| November 1852–March 1853 | |
| Franklin Pierce | William L. Marcy |
| 1853–1857 | March 1853–March 1857 |
| James Buchanan | Lewis Cass |
| 1857–1861 | March 1857–December 1860 |
| Jeremiah S. Black | |
| December 1860–March 1861 | |
| Abraham Lincoln | William H. Seward |
| 1861–1865 | March 1861–April 1865 |
| Andrew Johnson | William H. Seward |
| 1865–1869 | April 1865–March 1869 |
| Ulysses S. Grant | Elihu B. Washburne |
| 1869–1877 | March 1869 |
| Hamilton Fish | |
| March 1869–March 1877 | |
| Rutherford B. Hayes | William M. Evarts |
| 1877–1881 | March 1877–March 1881 |
| James Garfield | James G. Blaine |
| 1881 | March 1881–December 1881 |
| Chester Arthur | Frederick T. Frelinghuysen |
| 1881–1885 | December 1881–March 1885 |
| Grover Cleveland | Thomas F. Bayard |
| 1885–1889 | March 1885–March 1889 |
| Benjamin Harrison | James G. Blaine |
| 1889–1893 | March 1889–June 1892 |
| John W. Foster | |
| June 1892–February 1893 | |
| Grover Cleveland | Walter Q. Gresham |
| 1893–1897 | March 1893–May 1895 |
| Richard Olne | |
| June 1895–March 1897 | |
| William McKinley | John Sherman |
| 1897–1901 | March 1897–April 1898 |
| William R. Day | |
| April 1898–September 1901 | |
| John Hay | |
| September 1898–September 1901 | |
| Theodore Roosevelt | John Hay |
| 1901–1909 | September 1901–July 1905 |
| Elihu Root | |
| July 1905–January 1909 | |
| Robert Bacon | |
| January 1909–March 1909 | |
| William H. Taft | Philander C. Knox |
| 1909–1913 | March 1909–March 1913 |
| Woodrow Wilson | William Jennings Bryan |
| 1913–1921 | March 1913–June 1915 |
| Robert Lansing | |
| June 1915–February 1920 | |
| Bainbridge Colby | |
| March 1920–March 1921 | |
| Warren Harding | Charles Evans Hughes |
| 1921–1923 | March 1921–March 1923 |
| Calvin Coolidge | Charles Evans Hughes |
| 1923–1929 | March 1923–March 1925 |
| Frank B. Kellogg | |
| March 1925–March 1929 | |
| Herbert Hoover | Henry L. Stimson |
| 1929–1933 | March 1929–March 1933 |
| Franklin D. Roosevelt | Cordell Hull |
| 1933–1945 | March 1933–November 1944 |
| Edward R. Stettinius, Jr. | |
| December 1944–June 1945 | |
| Harry Truman | James F. Byrnes |
| 1945–1953 | July 1945–January 1947 |
| George C. Marshall | |
| January 1947–January 1949 | |
| Dean G. Acheson | |
| January 1949–January 1953 | |
| Dwight Eisenhower | John Foster Dulles |
| 1953–1961 | January 1953–April 1959 |
| Christian A. Herter | |
| April 1959–January 1961 | |
| John F. Kennedy | Dean Rusk |
| 1961–1963 | January 1961–November 1963 |
| Lyndon Johnson | Dean Rusk |
| 1963–1969 | November 1963–January 1969 |
| Richard Nixon | William P. Rogers |
| 1969–1974 | January 1969–September 1973 |
| Henry A. Kissinger | |
| September 1973–August 1974 | |
| Gerald Ford | Henry A. Kissinger |
| 1974–1977 | August 1974–January 1977 |
| Jimmy Carter | Cyrus Vance |
| 1977–1981 | January 1977–April 1980 |
| Edmund Muskie | |
| May 1980–July 1981 | |
| Ronald Reagan | Alexander Haig, Jr. |
| 1981–1989 | January 1981–July 1982 |
| George P. Shultz | |
| July 1982–January 1989 | |
| George H.W. Bush | James A. Baker, III |
| 1989–1993 | January 1989–August 1992 |
| Lawrence S. Eagleburger | |
| December 1992–January 1993 * | |
| William J. Clinton | Warren M. Christopher |
| 1993–2001 | January 1993–January 1997 |
| Madeleine Albright | |
| January 1997–January 2001 | |
| George W. Bush | Colin L. Powell |
| 2001– | January 2001–January 2005 |
| Condoleezza Rice | |
| January 2005– |
* Served as acting secretary of state, August-December 1992.