| Nº | Picture | Name | President | Term in office |
| Holders of the title "Wife of the President" |
|
| 1º |  | Mercedes Jijón | Juan José Flores | 1830–1834 |
|
| 2º |  | Baltazara Calderón de Rocafuerte | Vicente Rocafuerte y Bejarano | 1835–1839 |
|
| (1º) | | Mercedes Jijón | Juan José Flores | 1839–1845 |
|
|  | María Rosa Icaza | José Joaquín de Olmedo
(Head of the Provisional Government) | 1845–1845 |
|
| 3º | | Juana Andrade Fuente Fría | Vicente Ramón Roca | 1845–1849 |
|
|  | Carmen Salinas de la Vega | Manuel de Ascazubi y Matheu
(Vice-president, in charge of the Government) | 1849–1850 |
|
| 4º |  | Tomasa Carbo y Noboa | Diego Noboa | 1850–1851 |
|
| 5º |  | Teresa Jado | José María Urvina y Viteri | 1851–1856 |
|
| 6º |  | Carmen de Santistevan y Avilés | Francisco Robles Garcia | 1856–1859 |
|
| 7º | | Rosa Ascázubi y Matheu | Gabriel García Moreno | 1859–1865 |
|
| | Widower | Rafael Carvajal
(Vice-president, in charge of the Government) | 1865–1865 |
|
| 8º | | María Antonia Andrade | Jeronimo Carrion y Palacio | 1865–1867 |
|
| | Juana Arteta y Garzon | Pedro José de Arteta
(Vice-president, in charge of the Government) | 1867–1868 |
|
| | Single | Javier Espinosa y Espinosa | 1868–1869 |
|
|  | Mariana del Alcázar y Ascasubi | Gabriel García Moreno
(Interim President) | 1869–1869 |
|
| | Carmen Salinas de la Vega | Manuel de Ascásubi y Matheu
(Interim constitutional President) | 1869–1869 |
|
| 9º | | Mariana del Alcazar y Ascasubi | Gabriel García Moreno | 1869–1875 |
|
| | | Francisco Xavier León y Franco
(Vice-president, in charge of the Government) | 1875–1875 |
|
| | Isabel Valdivieso y Carcelén de Guevara | José Javier Eguiguren
(Min. of Finance, in charge of the Government) | 1875–1875 |
|
| 10º | | Rosa Lucía Moscoso Cardenas | Antonio Borrero y Cortázar | 1875–1876 |
|
| 11º |  | Marieta de Veintemilla | Ignacio de Veintemilla y Villacis | 1876–1883 |
|
|  | Jesús Dávila Heredia | Luis Cordero Crespo
(1st President of the Pentavirato) | 1883 |
|
| | Antonia Chiriboga y Muñoz | Rafael Pérez Pareja
(2nd President of the Pentavirato) | 1883 |
|
| 12º | | Pastoriza Marquez de la Plata y Plaza | José María Plácido Caamaño | 1883–1888 |
|
| | Leticia Escobar y Salvador | Pedro José Cevallos
(Vice-president, in charge of the Government) | 1895–1895 |
|
| 13º | | Leonor Ruiz de Apodaca | Antonio Flores Jijón | 1888–1892 |
|
| | Widower
(Jesús Davila Heredia) | Luis Cordero Crespo | 1892–1895 |
|
| | Manuela Quiñones Perez | Vicente Lucio Salazar
(Vice-president, in charge of the Government) | 1895–1895 |
|
| 14º |  | Ana Paredes Arosemena | Eloy Alfaro Delgado | 1895–1901 |
|
| 15º |  | Avelina Lasso | Leónidas Plaza y Gutiérrez | 1901–1905 |
|
| 16º | | Carmen Coello Alvarez | Lizardo García Sorroza | 1905–1906 |
|
| (14º) | | Ana Paredes Arosemena | Eloy Alfaro Delgado | 1906–1911 |
|
| | Rosa Elena Larrea y Gomez de la Torre | Carlos Freile Zaldumbide
(President of the Senate, in charge of the Government) | 1911–1911 |
|
| 17º |  | Lastenia Gamarra Menéndez | Emilio Estrada Carmona | 1911 |
|
| | Rosa Elena Larrea y Gomez de la Torre | Carlos Freile Zaldumbide
(President of the Senate, in charge of the Government) | 1911–1912 |
|
|
| | Victoria Malo German | Francisco Andrade Marín
(President of the Congress, in charge of the Government) | 1912–1912 |
|
| | Piedad Roca Marcos | Alfredo Baquerizo Moreno
(President of the Senate, in charge of the Government) | 1912–1912 |
|
| (15º) | | Avelina Lasso | Leónidas Plaza y Gutiérrez | 1912–1916 |
|
| 18º | | Piedad Roca Marcos | Alfredo Baquerizo Moreno | 1916–1920 |
|
| 19º |  | Esther Concha Torres | José Luis Tamayo | 1920–1924 |
|
| 20º | | Victoria Monsalve Cardenas | Gonzalo Córdova y Rivera | 1924–1925 |
|
| | Does not exist | Provisional Government | 1925–1926 |
|
| 21º |  | Laura Carbo Núñez | Isidro Ayora Cueva | 1926–1931 |
|
| | Lucy Lopez y Williams | Luis Larrea Alba
(Secretary of State, in charge of the Government) | 1931–1931 |
|
| | Piedad Roca Marcos | Alfredo Baquerizo Moreno
(President of the Senate, in charge of the Government) | 1931–1932 |
|
| | Manuela Gomez de la Torre y Nájera | Carlos Freile Larrea
(Secretary of State, in charge of the Government) | 1932–1932 |
|
| | Maria Elena Valenzuela y Plaza | Alberto Guerrero Martínez
(President of the Senate, in charge of the Government) | 1932–1932 |
|
| 22º | | Francisca Torres Lascano | Juan de Dios Martínez Mera | 1932–1933 |
|
| | | Abelardo Montalvo
(President of the Senate, in charge of the Government) | 1933–1934 |
|
| 23º | | Esther Silva Burbano | José María Velasco Ibarra | 1934–1935 |
|
| | Single | Antonio Pons
(Secretary of State, in charge of the Government) | 1935–1935 |
|
| | Adelina Espinosa García | Federico Páez
(Interim President) | 1935–1937 |
|
| | Mariana Calderón Alava | Alberto Enríquez Gallo
(Supreme Chief) | 1937–1938 |
|
| | Ana Maria Bustamante | Manuel María Borrero
(Interim President) | 1938 |
|
| 24º | | Judith Perez Davalos | Aurelio Mosquera Narváez | 1938–1939 |
|
|  | Elena Yerovi Matheu | Carlos Arroyo del Río
(President of the Senate, in charge of the Government) | 1939 |
|
| | Rosario Galarza Arizaga | Andres Fernandez de Cordova
(President of the Congress, in charge of the Government) | 1939–1940 |
|
| | | Julio Enrique Moreno
(President of the Senate, in charge of the Government) | 1940 |
|
| 25º | | Elena Yerovi Matheu | Carlos Arroyo del Río | 1940–1944 |
|
| | Does not exist | Provisional Government | 1944 |
|
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