Picture | Name | Entered office | Exited office | Notes | Appointed by |
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| Pedro de Valdivia | 11 June 1540 | December 1547 | | Charles V |
| Francisco de Villagra | December 1547 | 20 July 1549 | |
| Pedro de Valdivia | 20 July 1549 | 25 December 1553 | Killed at the Battle of Tucapel. |
| Rodrigo de Quiroga | 25 December 1553 | February 1555 |
| Francisco de Villagra | Triumvirate |
| Francisco de Aguirre |
| Cabildos of Chile | February 1555 | 23 May 1556 | The cities of Chile governed themselves while the dispute over the governorship was settled by the Real Audiencia in Lima. |
| Philip II |
| Francisco de Villagra | 23 May 1556 | April 1557 | |
| García Hurtado de Mendoza | April 1557 | February 1561 | |
| Francisco de Villagra | February 1561 | June 1563 | |
| Pedro de Villagra | June 1563 | June 1565 | |
| Rodrigo de Quiroga | June 1565 | August 1567 | |
| Real Audiencia of Chile | August 1567 | August 1568 | |
| Melchor Bravo de Saravia | August 1568 | January 1575 | |
| Rodrigo de Quiroga | January 1575 | February 1580 | |
| Martín Ruiz de Gamboa | February 1580 | July 1583 | |
| Alonso de Sotomayor | September 1583 | July 1592 | |
| Pedro de Viscarra | July 1592 | October 1592 | |
| Martín García Óñez de Loyola | October 1592 | December 1598 | Killed at the Disaster of Curalaba |
| Philip III |
| Pedro de Viscarra de la Barrera | December 1598 | May 1599 | |
| Francisco de Quiñónez | May 1599 | July 1600 | |
| Alonso García de Ramón | July 1600 | February 1601 | |
| Alonso de Ribera de Pareja | February 1601 | March 1605 | |
| Alonso García de Ramón | March 1605 | 2 September 1610 | |
| Luis Merlo de la Fuente Ruiz de Beteta | 2 September 1610 | January 1611 | |
| Juan Jaraquemada | January 1611 | 27 March 1612 | |
| Alonso de Ribera de Pareja | 27 March 1612 | 9 March 1617 | |
| Fernando Talaverano Gallegos | 9 March 1617 | 14January 1618 | |
| Lope de Ulloa y Lemos | 14 January 1618 | 8 December 1620 | |
| Cristóbal de la Cerda y Sotomayor | 8 December 1620 | November 1621 | |
| Philip IV |
| Pedro Osores de Ulloa | November 1621 | September 1624 | |
| Francisco de Álava y Nureña | September 1624 | May 1625 | |
| Luis Fernández de Córdoba y Arce | May 1625 | December 1629 | |
| Francisco Laso de la Vega | December 1629 | May 1639 | |
| Francisco López de Zúñiga 2nd Marquis of Baides | May 1639 | May 1646 | |
| Martín de Mujica y Buitrón | May 1646 | April 1649 | |
| Alonso de Figueroa y Córdoba | April 1649 | May 1650 | |
| Francisco Antonio de Acuña Cabrera y Bayona | May 1650 | January 1656 | |
| Pedro Porter Casanate | January 1656 | February 1662 | |
| Diego González Montero Justiniano | February 1662 | May 1662 | |
| Ángel de Peredo | May 1662 | January 1664 | |
| Francisco de Meneses Brito | January 1664 | 1667 | |
| Charles II |
| Diego Dávila Coello y Pacheco 1st Marquis of Navamorcuende | 1667 | February 1670 | |
| Diego González Montero Justiniano | February 1670 | October 1670 | |
| Juan Henríquez de Villalobos | October 1670 | April 1682 | |
| Marcos José de Garro Senei de Artola | April 1682 | January 1692 | |
| Tomás Marín de Poveda 1st Marquis of Cañada Hermosa | January 1692 | December 1700 | |
| Philip V |
| Francisco Ibáñez de Segovia y Peralta | December 1700 | February 1709 | |
| Juan Andrés de Ustariz | February 1709 | December 1716 | |
| José de Santiago Concha y Salvatierra | December 1716 | 17 December 1717 | |
| | 17 December 1717 | 11 November 1733 | |
Gabriel Cano y Aponte | Luis I |
| |
| Francisco de Sánchez de la Barreda | 11 November 1733 | May 1734 | |
| Manuel Silvestre de Salamanca Cano | May 1734 | November 1737 | |
| José Antonio Manso de Velasco Count of Superunda | November 1737 | June 1744 | |
| Francisco José de Ovando 1st Marquis of Brindisi | June 1745 | 25 March 1746 | |
| Domingo Ortíz de Rosas 1st Marquis of Poblaciones | 25 March 1746 | 28 December 1755 | |
| Ferdinand VI |
| Manuel de Amat y Junyent | 28 December 1755 | 9 September 1761 | |
| Charles III |
| Félix de Berroeta | September 1761 | October 1762 | |
| Antonio de Guill y Gonzaga | October 1762 | August 1768 | |
| Juan de Balmaseda | August 1768 | March 1770 | |
| Francisco Javier de Morales | March 1770 | March 1772 | |
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