The office of State Superintendent of Public Instruction was created in 1835. By Legislative Act in 1843, which went in effect in 1844, the office was abolished. The following Superintendents were elected by the Legislature:
| Robert H. McEwen | 1835-1840 |
| Robert P. Currin | 1840-1841 |
| Scott Terry | 1841-1844 |
From 1844 to 1867, the State Treasurer was ex-officio Superintendent of Public Instruction. In 1867, the office was again created. The following Superintendents were elected by the people and served for the respective periods shown below:
| John Eaton, Jr. | 1867-1869 |
| A. J. Tipton | 1869-1871 |
In 1870, the office was again abolished, and the duties devolved upon the State Treasurer, who was made ex-officio Superintendent of Public Instruction. In 1873, the office was recreated, and the following officers, appointed by the Governor and confirmed by the Senate, have served the terms shown below:
| J. B. Killebrew* | |
| John M. Flemings | 1873-1875 |
| Leon Trousdale | 1875-1881 |
| W. S. Doak | 1881-1882** |
| Julia A. Doak | 3 mos. ending July, 1882*** |
| G. S. Crawford | 1882-1883*** |
| Thomas H. Paine | 1883-1887 |
| Frank M. Smith | 1887-1891 |
| W. R. Garrett | 1891-1893 |
| S. G. Gilbreath | 1895-1897 |
| Price Thomas | 1897-1899 |
| Morgan C. Fitzpatrick | 1899-1903 |
| Seymour A. Mynders | 1903-1907 |
| R. L. Jones | 1907-1911 |
| J. W. Brister | 1911-1913 |
| S. J. Thompson | 1913-1915*** |
| S. W. Sherrill | 1915-1919 |
| Albert Williams | 1919-1921 |
| J. B. Brown | 1921-1923 |
Under the reorganization bill of 1923, the State Department of Public Instruction became the State Department of Education.
The title of the chief state school officer was changed to Commissioner of Education.
| P. L. Harned | 1923-1933 |
| Walter D. Cocking | 1933-1937 |
| W. A. Bass | 1937-1938 |
| J. M. Smith | 1938 |
| Halbert Harville | 1938-1939 |
| B. O. Duggan | 1939-1945 |
| Burgin E. Dossett | 1945-1949 |
| J. M. Smith | 1949-1950 |
| J. A. Barksdale | 1950-1953 |
| Quill E. Cope | 1953-1958 |
| Joe Morgan | 1958-1963 |
| J. H. Warf | 1963-1971 |
| E. C. Stimbert | 1971-1972 |
| Benjamin E. Carmichael | 1972-1975 |
| Sam H. Ingram | 1975-1979 |
| Otis L. Floyd | 1979 |
| E. A. Cox | 1979-1980 |
| Robert L. McElrath | 1981-1987 |
| Charles E. Smith | 1987-1993 |
| Wayne Qualls | 1994-1995 |
| Jane Walters | 1995-1999 |
| E. Vernon Coffey | 1999-2001 |
| Faye P. Taylor | 2001-2003 |
| Lana C. Seivers | 2003-2008 |