| No. | Portrait | Governor | From | Until | Secretary of the Indies[1] | Valido Secretary of the Universal Bureau First Secretary of State | Monarch |
| 1 | | Antonio de Mendoza | 14 November 1535 | 25 November 1550 | Vacant (Overseas Affairs hold by the President of the Council of the Indies) | No valido |  Charles I |
| 2 | | Luís de Velasco | 25 November 1550 | 31 July 1564 |
 Philip II |
| Int. | | Francisco Ceinos, Dean of the Audiencia | 1 August 1564 | 19 October 1566 |
| 3 | | Gastón Carrillo de Peralta y Bosquete, 3rd Marquess of Falces | 19 October 1566 | 11 November 1567 |
| Acting | | Alonso de Muñoz, Royal commissioner of New Spain | 11 November 1567 | 15 April 1568 |
Luis Carrillo, Royal commissioner of New Spain |
Francisco Ceinos, Dean of the Audiencia | 15 April 1568 | 5 November 1568 |
| 4 | | Martín Enríquez de Almanza | 5 November 1568 | 4 October 1580 |
| 5 | | Lorenzo Suárez de Mendoza, 4th Count of La Coruña | 4 October 1580 | 19 June 1583 |
| Int. | | Luis de Villanueva y Zapata, Dean of the Audiencia | 19 June 1583 | 25 September 1584 |
| 6 | | Pedro de Moya y Contrerás (Archbishop of Mexico) | 25 September 1584 | 17 October 1585 |
| 7 | | Álvaro Manrique de Zúñiga 1st Marquess of Villamanrique | 17 October 1585 | 27 January 1590 |
| 8 | | Luís de Velasco Marquess of Salinas | 27 January 1590 | 5 November 1595 |
| 9 | | Gaspar de Zúñiga Acevedo y Fonseca, 5th Count of Monterrey | 5 November 1595 | 27 October 1603 |
Duke of Lerma[2] | Philip III |
| 10 | | Juan de Mendoza y Luna, Marquess of Montesclaros | 27 October 1603 | 2 July 1607 |
| 11 | | Luís de Velasco, Marquess of Salinas | 2 July 1607 | 19 June 1611 |
| 12 | | García Guerra, O.P. (Archbishop of Mexico) | 19 June 1611 | 22 February 1612 |
| Int. | | Pedro Otárola, Dean of the Audiencia | 22 February 1612 | 18 October 1612 |
| 13 | | Diego Fernández de Córdoba, Marquess of Guadalcázar and Count of Posadas | 18 October 1612 | 14 March 1621 |
Cristóbal Gómez de Sandoval[2] |
| Acting | | Paz de Valecillo, Dean of the Audiencia | 14 March 1621 | 11 September 1621 |
Philip IV |
Baltasar de Zúñiga[2] |
| 14 | | Diego Carrillo de Mendoza y Pimentel, 1st Marquess of Gélves | 21 September 1621 | 1 November 1624 |
Count-Duke of Olivares[2] |
Vacant Due to the discrepancy on the arrival of successor Viceroy from 1 to 3 November 1624. |
| 15 | | Rodrigo Pacheco y Osorio de Toledo, 3rd Marquess of Cerralvo | 3 November 1624 | 16 September 1635 |
| 16 | | Lope Díez de Aux de Armendáriz, Marquess of Cadreita | 16 September 1635 | 28 August 1640 |
| 17 | | Diego Roque López Pacheco Cabrera y Bobadilla, 7th Duke of Escalona, 7th Marquess of Villena and 7th Count of Xiquena | 28 August 1640 | 10 June 1642 |
| 18 | | Juan de Palafox y Mendoza (Bishop of Puebla) | 10 June 1642 | 23 November 1642 |
| 19 | | García Sarmiento de Sotomayor, 2nd Count of Salvatierra and Marquess of Sobroso | 23 November 1642 | 14 May 1648 |
Luis de Haro[2] |
| 20 | | Marcos de Torres y Rueda (Bishop of Yucatan) | 15 May 1648 | 22 April 1649 |
| Int. | | Matías de Peralta, Dean of the Audiencia | 22 April 1649 | 28 June 1650 |
| 21 | | Luis Enríquez de Guzmán, 9th Count of Alba de Liste and Marquess of Villaflor | 28 June 1650 | 15 August 1653 |
| 22 | | Francisco Fernández de la Cueva, 8th Duke of Alburquerque, Marquess of Cuéllar, Count of Ledesma and of Huelma | 15 August 1653 | 16 September 1660 |
| 23 | | Juan de Leyva de la Cerda, Marquess of Adrada | 16 September 1660 | 29 June 1664 |
| No valido[3] |
| 24 | | Diego Osorio de Escobar y Llamas (Bishop of Puebla) | 29 June 1664 | 15 October 1664 |
| 25 | | Antonio Sebastián de Toledo Molina y Salazar, 2nd Marquess of Mancera | 16 October 1664 | 20 November 1673 |
Juan Everardo Nithard[2] |  Charles II |
Fernando de Valenzuela[2] |
| 26 | | Pedro Nuño Colón de Portugal y Castro, 6th Duke of Veragua, 6th Marquess of Jamaica and 6th Count of Gelves | 20 November 1673 | 13 December 1673 |
| 27 | | Payo Enríquez de Rivera Manrique, O.S.A. (Bishop of Guatemala and Archbishop of Mexico) | 13 December 1673 | 7 November 1680 |
John Joseph of Austria[4] |
Duke of Medinaceli[4] |
| 28 | | Tomás Antonio Manuel Lorenzo de la Cerda y Aragón 3rd Marquess of La Laguna de Camero Viejo | 7 November 1680 | 16 June 1686 |
| Count of Oropesa[4] |
| 29 | | Melchor Portocarrero y Lasso de la Vega, 3rd Count of Monclova | 16 June 1686 | 20 November 1688 |
| 30 | | Gaspar Melchor Baltasar de la Cerda Silva Sandoval y Mendoza, 8th Count of Galve, Lord of Salcedón and Tortola | 20 November 1688 | 27 February 1696 |
Cardinal Portocarrero[2] |
| 31 | | Juan de Ortega Cano Montañez y Patiño (Bishop of Durango, Guatemala, Michoacán and Archbishop of Mexico) | 27 February 1696 | 18 December 1696 |
| 32 | | José Sarmiento Valladares Arines de Romay, 1st Duke of Atrisco, Count of Moctezuma and of Tula | 18 December 1696 | 4 November 1701 |
| Count of Oropesa[4] |
Cardinal Portocarrero[2] |
| Antonio de Ubilla[5] |  Philip V |
| 33 | | Juan de Ortega Cano Montañez y Patiño (Archbishop of Mexico) | 4 November 1701 | 27 November 1702 |
| 34 | | Francisco V Fernández de la Cueva Enríquez y Fernández de la Cueva, 10th Duke of Alburquerque and Marquess of Cuéllar | 27 November 1702 | 13 November 1710 |
| Marquis of Mejorada del Campo[5] |
| 35 | | Fernando de Alencastre Noroña y Silva, 1st Duke of Linares and Marquess of Valdefuentes | 13 November 1710 | 16 July 1716 |
| Manuel de Vadillo y Velasco[5] |
José de Grimaldo[5] |
| Bernardo Tinajero de la Escalera[6] |
| No secretary |
| 36 | | Baltasar de Zúñiga Guzmán Sotomayor y Mendoza, 1st Duke of Arión and Marquess of Valero | 16 July 1716 | 15 October 1722 |
 Miguel Fernández Durán[6] |
| Andres Matías de Pes Marzaraga[6] |
| 37 | | Juan de Acuña y Bejarano, 2nd Marquess of Casa Fuerte | 15 October 1722 | 17 March 1734 |
| No secretary |
| Antonio de Sopeña y Mioño[6] |
| Juan Bautista de Orendáin[5] | |
 Louis I From 1700 to 1724, Philip V was the king; then from 1724 to 1746. Louis I only reigned in 1724. |
José de Grimaldo[5] |  Philip V |
Baron Ripperda[5] |
José de Grimaldo[5] |
José de Patiño y Rosales[6] |
| Juan Bautista de Orendáin[5] |
| 38 | | Juan Antonio de Vizarrón y Eguiarreta (Archbishop of Mexico) | 17 March 1734 | 17 August 1740 |
José de Patiño y Rosales[7] |
| Mateo Pablo Díaz de Lavandero[6] | Marquess of Villarías[7] |
Marquess of Villarías[6] |
| 39 | | Pedro de Castro Figueroa y Salazar, 1st Duke of La Conquista and 1st Marquess of Gracia Real | 17 August 1740 | 22 August 1741 |
| Int. | | Pedro Malo de Villavicencio, President of the Audiencia | 23 August 1741 | 2 November 1742 |
| 40 | | Pedro Cebrián y Agustín, 5th Count of Fuenclara | 3 November 1742 | 9 July 1746 |
Marquess of Ensenada[6] |
| 41 | | Juan Francisco de Güemes y Horcasitas, 1st Count of Revillagigedo | 9 July 1746 | 9 November 1755 | .jpg) Ferdinand VI |
José de Carvajal[7] |
Duke of Huéscar (Interim)[7] |
Ricardo Wall[7] |
Ricardo Wall (Interim)[8] |
| Julián de Arriaga y Ribera[8] |
| 42 | | Agustín de Ahumada y Villalón, Marquess of Amarillas | 10 November 1755 | 5 February 1760 |
 Charles III |
| Int. | | Francisco Antonio de Echávarri, Dean of the Audiencia | 5 February 1760 | 28 April 1760 |
| 43 | | Francisco Cajigal de la Vega | 28 April 1760 | 5 October 1760 |
| 44 | | Joaquín de Montserrat, Marquess of Cruillas | 5 October 1760 | 24 August 1766 |
Jerónimo Grimaldi[7] |
| 45 | | Carlos Francisco de Croix, Marquess of Croix | 24 August 1766 | 22 September 1771 |
| 46 | | Antonio María de Bucareli y Ursúa | 22 September 1771 | 9 April 1779 |
Marquess of Sonora[8] |
Count of Floridablanca[7] |
| Int. | | Francisco Romá y Rosell, Regent of the Audiencia | 10 April 1779 | 22 August 1779 |
| 47 | | Martín de Mayorga Ferrer, Captain General of Guatemala | 23 August 1779 | 28 April 1783 |
| 48 | | Matías de Gálvez y Gallardo, Captain General of Guatemala | 28 April 1783 | 20 October 1784 |
| – | | Vicente de Herrera y Rivero, Regent of the Audiencia | 20 October 1784 | 17 June 1785 |
| 49 | | Bernardo de Gálvez y Madrid, 1st Viscount of Galveston and 1st Count of Gálvez | 17 June 1785 | 30 November 1786 |
| Int. | | Eusebio Sánchez Pareja y Beleño Regent of the Audiencia | 30 November 1786 | 8 May 1787 |
| 50 | | Alonso Núñez de Haro y Peralta (Archbishop of Mexico) | 8 May 1787 | 16 August 1787 |
Count of Floridablanca (Interim)[8] |
Antonio Porlier[9] Antonio Valdés y Fernández Bazán[10] |
| 51 | | Manuel Antonio Flórez Maldonado | 16 August 1787 | 16 October 1789 |
| 52 | | Juan Vicente de Güemes Pacheco de Padilla y Horcasitas, 2nd Count of Revillagigedo | 17 October 1789 | 11 July 1794 |
 Charles IV |
| No secretary (affairs of Indies distributed among different secretariats) | Count of Aranda (Interim)[7] |
Manuel Godoy[7] |
| 53 | | Miguel de la Grúa Talamanca de Carini y Branciforte, 1st Marquess of Branciforte | 12 July 1794 | 31 May 1798 |
Francisco de Saavedra[7] |
| 54 | | Miguel José de Azanza Alegría, 1st Duke of Santa Fe | 31 May 1798 | 30 April 1800 |
Mariano Luis de Urquijo[7] |
| 55 | | Félix Berenguer de Marquina | 30 April 1800 | 4 January 1803 |
Pedro Cevallos Guerra[7] |
| 56 | | José de Iturrigaray[11] | 4 January 1803 | 16 September 1808 |
Gonzalo O'Farril[7] |
Pedro Cevallos Guerra[7] | Ferdinand VII |
Miguel José de Azanza[12] | Mariano Luis de Urquijo[7] |  Joseph I[13] |
| 57 | | Pedro de Garibay[11] | 16 September 1808 | 19 July 1809 |
| 58 | | Francisco Javier de Lizana y Beaumont (Archbishop of Mexico)[11] | 19 July 1809 | 8 May 1810 |
| 59 | | Pedro Catani[11] | 8 May 1810 | 14 September 1810 |
| 60 | | Francisco Javier Venegas, 1st Marquess of Reunión and of New Spain[11] | 14 September 1810 | 4 March 1813 |
| 61 | | Félix María Calleja del Rey, 1st Count of Calderón[11] | 4 March 1813 | 20 September 1816 |
| No secretary | Juan O'Donoju(Interim)[7] |
| Fernando de Laserna (Interim)[7] |
| Manuel Antonio de la Bodega y Mollinedo[14] | José Luyando (Interim)[7] | Ferdinand VII |
Miguel de Lardizabal[14] | José Miguel de Carvajal-Vargas[7] |
Pedro Cevallos Guerra[7] |
| No secretary | Jaun Estebán Lozano de Torres[7] |
Pedro Cevallos Guerra[7] |
| 62 | | Juan Ruiz de Apodaca, 1st Count of Venadito | 20 September 1816 | 5 July 1821 |
José García de León[7] |
Carlos Martínez de Irujo (Interim)[7] |
Manuel González Salmón (Interim)[7] |
Joaquín José Melgarejo[7] |
| Antonio González Salmón (Interim)[14] |
| Juan Jabat Aztal[7] |
Antonio Porcel Román[14] |
Evaristo Pérez de Castro[7] |
| Ramón Gil de la Cuadra[14] |
| Antonio de Guilleman (Interim)[14] | Joaquín Anduaga Cuenca (Interim)[7] |
| Francisco de Paula Escudero (Interim)[7] |
| Ramón Olaguer Feliú[14] |
Eusebio Bardají y Azara[7] |
| Ramón López Pelegrín[14] |
| 63 | | Francisco Novella Azabal Pérez y Sicardo | 15 July 1821 | 21 July 1821 |
| 64 | | Juan O'Donojú | 21 July 1821 | 28 September 1821 |