| Term start | Term end | Name | Political Party |
| 19 June 1826 | 18 April 1828 | Antonio José de Sucre | Military |
| 18 April 1828 | 2 August 1828 | José María Pérez de Urdininea | Military |
| 2 August 1828 | 18 December 1828 | José Miguel de Velasco Franco (1st time, acting) | Military |
| 18 December 1828 | 31 December 1828 | Pedro Blanco (provisional) | Military |
| 1 January 1829 | 24 May 1829 | José Miguel de Velasco Franco (2nd time, "accidental") | Military |
| 24 May 1829 | 20 February 1839 | Andrés de Santa Cruz (provisional to 15 August 1831; also Supreme Protector of the Peru-Bolivian Confederation 28 October 1836 - 20 February 1839) | Military |
| 20 February 1839 | 10 June 1841 | José Miguel de Velasco Franco (3rd time) (Provisional Supreme Chief to 16 June 1839, provisional to 15 August 1840) | Military |
| 10 June 1841 | 9 July 1841 | Sebastián Ágreda (Provisional Chief) | Military |
| 9 July 1841 | 22 September 1841 | Mariano Calvo (acting) | Military |
| 22 September 1841 | 23 December 1847 | José Ballivián (provisional to 15 August 1844) | Military |
| 23 December 1847 | 2 January 1848 | Eusebio Guilarte Vera (interim) | Military |
| 6 January 1848 | 18 January 1848 | Manuel Isidoro Belzu (1st time, interim) | Populist Party |
| 18 January 1848 | 6 December 1848 | José Miguel de Velasco Franco (4th time, provisional) | Military |
| 6 December 1848 | 15 August 1855 | Manuel Isidoro Belzu (2nd time) (provisional (in rebellion from 13 October 1848) to 15 August 1850) | Populist Party |
| 15 August 1855 | 21 October 1857 | Jorge Córdova | Populist Party |
| 21 October 1857 | 14 January 1861 | José María Linares (provisional (in rebellion from 9 September 1857)) | Generator Party |
| 14 January 1861 | 4 May 1861 | Military junta composed of: Ruperto Fernández José María Achá Manuel Antonio Sánchez (to 9 Apr 1861) | Military |
| 4 May 1861 | 28 December 1864 | José María Acha (provisional to 15 August 1862) | Military |
| 28 December 1864 | 15 January 1871 | Mariano Melgarejo (provisional to 15 August 1870) | Military |
| 15 January 1871 | 27 November 1872 | Agustín Morales (Supreme Chief of the Revolution (in rebellion from 26 November 1870) to 21 January 1871; provisional to 25 August 1872) | Liberal Party |
| 27 November 1872 | 28 November 1872 | Juan de Dios Bosque (acting) | Non-party |
| 28 November 1872 | 9 May 1873 | Tomás Frías Ametller (1st time) | Liberal Party |
| 9 May 1873 | 14 February 1874 | Adolfo Ballivián | Military |
| 14 February 1874 | 4 May 1876 | Tomás Frías Ametller (2nd time) | Liberal Party |
| 4 May 1876 | 28 December 1879 | Hilarión Daza (provisional) | Military |
| 28 December 1879 | 17 January 1880 | Uladislao Silva (President of Junta) | Military |
| 19 January 1880 | 31 May 1880 | Narciso Campero (1st time, provisional) | No Party |
| 31 May 1880 | 19 June 1880 | Aniceto Arce (1st time, acting) | Conservative Party |
| 19 June 1880 | 3 September 1884 | Narciso Campero (2nd time, interim from 6 August 1884) | Conservative Party |
| 3 September 1884 | 15 August 1888 | Gregorio Pacheco | Conservative Party |
| 15 August 1888 | 11 August 1892 | Aniceto Arce (2nd time) | Conservative Party |
| 11 August 1892 | 19 August 1896 | Mariano Baptista | Conservative Party |
| 19 August 1896 | 12 April 1899 | Severo Fernández | Conservative Party |
| 12 April 1899 | 25 October 1899 | Serapio Reyes Ortiz (President of Federal Junta (in rebellion from 12 December 1898)) | Liberal Party |
| 25 October 1899 | 14 August 1904 | José Manuel Pando (interim from 6 August 1904) | Liberal Party |
| 14 October 1904 | 12 October 1909 | Ismael Montes (1st time) | Liberal Party |
| 12 October 1909 | 14 October 1913 | Eliodoro Villazón | Liberal Party |
| 14 October 1913 | 15 October 1917 | Ismael Montes (2nd time) | Liberal Party |
| 15 October 1917 | 12 July 1920 | José Gutiérrez | Liberal Party |
| 12 July 1920 | 13 July 1920 | Bautista Saavedra (1st time, "Political Chief") | Republican Party |
| 13 July 1920 | 28 January 1921 | Military junta composed of: José María Escalier Bautista Saavedra José Manuel Ramírez | Republican Party |
| 28 January 1921 | 3 September 1925 | Bautista Saavedra | Republican Party |
| 3 September 1925 | 10 January 1926 | Felipe S. Guzmán (provisional) | Republican Party |
| 10 January 1926 | 28 May 1930 | Hernando Siles Reyes | Republican Party |
| 28 May 1930 | 25 June 1930 | Council of Ministers (acting) composed of: Alberto Díez de Medina Germán Antelo Arauz (to 17 Jun 1930) Franklin Mercado David Toro José Aguirre Achá Fidel Vega Carlos Banzer Ezequiel Romecín Calderón (from 17 Jun 1930) | |
| 28 June 1930 | 5 March 1931 | Carlos Blanco Galindo (Chairman of the Military Government Junta) | Military |
| 5 March 1931 | 27 November 1934 | Daniel Salamanca Urey | Republican Party |
| 28 November 1934 | 17 May 1936 | José Luis Tejada Sorzano | Liberal Party |
| 17 May 1936 | 20 May 1936 | Germán Busch (1st time, Provisional Chairman of the Government Junta) | Military |
| 20 May 1936 | 13 July 1937 | David Toro (Chairman of the Government Junta) | Military |
| 13 July 1937 | 23 August 1939 | Germán Busch (2nd time, Chairman of the Government Junta to 28 May 1938) | Military |
| 23 August 1939 | 15 April 1940 | Carlos Quintanilla (Provisional) | Military |
| 15 April 1940 | 20 December 1943 | Enrique Peñaranda | Military |
| 20 December 1943 | 21 July 1946 | Gualberto Villarroel López (Chairman of the Government Junta to 5 April 1944; Provisional president 5 April - 6 August 1944) | Military/Fatherland's Cause-Nationalist Revolutionary Movement |
| 21 July 1946 | 15 August 1946 | Néstor Guillén (Senior Judge to 22 July 1946, then Chairman of the Provisional Government Junta) | Non-party |
| 15 August 1946 | 10 March 1947 | Tomás Monje (Chairman of the Provisional Government Junta) | Non-party |
| 10 March 1947 | 22 October 1949 | Enrique Hertzog | Socialist Republican Union Party |
| 22 October 1949 | 16 May 1951 | Mamerto Urriolagoitia (acting (for Hertzog from 7 May 1949) to 24 October 1949) | Socialist Republican Union Party |
| 16 May 1951 | 11 April 1952 | Hugo Ballivián (Chairman of the Military Junta) | Military |
| 11 April 1952 | 16 April 1952 | Hernán Siles Zuazo (1st time, Provisional) | Nationalist Revolutionary Movement |
| 16 April 1952 | 6 August 1956 | Víctor Paz Estenssoro (1st time) | Nationalist Revolutionary Movement |
| 6 August 1956 | 6 August 1960 | Hernán Siles Zuazo (2nd time) | Nationalist Revolutionary Movement |
| 6 August 1960 | 4 November 1964 | Víctor Paz Estenssoro (2nd time) | Nationalist Revolutionary Movement |