Mission Start | Mission End | Name | Notes |
|---|
| 1475 | 1475 | Gonzalo Fernández de Heredia | |
| 1482 | 1484 | Gonzalo de Beteta | |
| 1485 | 1487 | Íñigo López de Mendoza, Count of Tendilla | |
| 1488 | 1491 | Francisco de Rojas y Escobar | |
| 1494 | 1499 | Garcilaso de la Vega, Señor de los Arcos | |
| 1498 | 1507 | Francisco de Rojas y Escobar | |
| 1507 | 1520 | Jerónimo Vich y Valterra | |
| 1520 | 1522 | Juan Manuel, señor de Belmonte | |
| 1522 | 1526 | Luis Fernández de Córdoba y Zúñiga | |
| 1537 | 1540 | Juan Fernández Manrique de Lara, Marquess of Aguilar de Campoo | |
| 1558 | 1558 | Pedro Téllez-Girón y de la Cueva, Count of Ureña | |
| 1561 | 1562 | Luis de Zúñiga y Requesens | |
| 1566 | 1566 | Luis Fernández-Manrique de Lara, Marquess of Aguilar de Campoo | Ambassador Extraordinary sent by Philip II to congratulate Pope Pius V on his election. |
| 1566 | 1571 | Antonio Perrenot de Granvela | |
| 1587 | 1587 | Enrique de Guzmán y Ribera, 2nd Count of Olivares | |
| 1588 | 1590 | Juan Vich y Manrique de Lara | |
| 1590 | 1603 | Antonio Fernández de Córdoba y Cardona, 5th Duke of Sessa | [2] |
| 1603 | 1606 | Juan Fernandez Pacheco, 5th Duke of Escalona | [2] |
| 1606 | 1609 | Gastón de Moncada, 2nd Marquis of Aitona | [2] |
| 1609 | 1616 | Francisco Ruiz de Castro | [2] |
| 1616 | 1619 | Gaspar de Borja y Velasco | Again ambassador from 1631 to 1633. |
| 1619 | 1623 | Francisco Fernández de la Cueva, 7th Duke of Alburquerque | [2] |
| 1623 | 1626 | Ruy III Gómez de Silva y Mendoza, 3rd Duke of Pastrana | [2] |
| 1625 | 1626 | Fernando Afán de Ribera y Téllez-Girón, 3rd Duke of Alcalá | Extraordinary appointed by Philip IV |
| 1626 | 1628 | Íñigo Vélez de Guevara y Tassis, 7th Count of Oñate | [2] |
| 1628 | 1631 | Manuel de Acevedo y Zúñiga, 6th Count of Monterrey | [2] |
| 1631 | 1631 | Diego de Saavedra Fajardo | |
| 1631 | 1633 | Gaspar de Borja y Velasco | Second term. [2] |
| 1633 | 1641 | Manuel de Moura y Corte-Real, 2nd Marquess of Castel-Rodrigo | [2] [3] |
| 1633 | 1637 | Domingo Pimentel | Ambassadors Extraordinary, sent by Philip IV to protest against the damages that Spain received from Rome. [4] |
| 1633 | 1643 | Juan Chumacero Carrillo y Sotomayor |
| 1641 | 1644 | Pedro III Fajardo, 5th Marquis of Los Vélez | [2] [5] |
| 1644 | 1645 | Juan Velasco de la Cueva y Pacheco, 7th Count of Siruela | [2] |
| 1646 | 1648 | Íñigo Vélez de Guevara, 8th Count of Oñate | [2] |
| 1649 | 1651 | Rodrigo Díaz de Vivar Mendoza y Sandoval, 7th Duke of the Infantado | [2] |
| 1652 | 1654 | Duarte Fernando Álvarez de Toledo, 7th Count of Oropesa | [6] |
| 1654 | 1657 | Diego de Aragón Tagliavia, 4th Duke of Terranova | [2] |
| 1657 | 1661 | Luis de Guzmán Ponce de Leon | [2] [7] |
| 1661 | 1664 | Pascual de Aragón | Cardinal [8] |
| 1662 | 1666 | Pedro Antonio de Aragón | Brother of the previous Ambassador. [2] [9] |
| 1667 | 1672 | Antonio Pedro Sancho Dávila y Osorio, 10th Marquess of Astorga | [2] [10] |
| 1672 | 1682 | Gaspar Méndez de Haro, 7th Marquess of Carpio | Absent between 1672 and 1676. [2] [11] |
| 1687 | 1696 | Luis Francisco de la Cerda, 9th Duke of Medinaceli | [2] |
| 1696 | 1698 | Luis Moscoso Ossorio, Count of Altamira | [2] |
| 1699 | 1709 | Juan Francisco Pacheco Téllez-Girón, Duke of Uceda | |
| 1708 | 1714 | Hercule-Louis Turinetti | Represented the Austrian Archduke Charles, which the Pope had recognized as King of Spain. |
| 1717 | 1725 | Francesco Acquaviva d'Aragona | |
| 1726 | 1732 | Marco Cornelio Bentivoglio | [12] |
| 1732 | 1734 | Luis Antonio de Belluga y Moncada | |
| 1735 | 1747 | Troiano Acquaviva d'Aragona | [13] |
| 1747 | 1748 | Alfonso Clemente de Aróstegui | |
| 1748 | 1760 | Joaquín Fernández Portocarrero | [14] |
| 1760 | 1765 | Manuel de Roda y Arrieta | |
| 1765 | 1772 | Tomás de Azpuru Ximénez | Archbishop of Valencia (1770) |
| 1772 | 1776 | José Moñino y Redondo, Conde de Floridablanca | |
| 1777 | 1784 | Jerónimo Grimaldi, Marquess of Grimaldi | |
| 1784 | 1798 | José Nicolás de Azara | |
| 1801 | 1809 | Antonio Vargas Laguna | |
| 1821 | 1824 | José Narciso de Aparici Soler | [15] |
| 1824 | 1826 | Guillermo Curtoys y Hunt | [15] |
| 1827 | 1831 | Pedro Gómez Labrador, Marqués de Labrador | [15] |
| 1843 | 1844 | Julián Villalba García | [15] |
| 1844 | 1847 | José del Castillo y Ayensa | [16] |
| 1847 | Joaquín Francisco Pacheco | [17] |
| 1847 | 1851 | Francisco Martínez de la Rosa | [17] |
| 1851 | 1852 | Salvador de Cea Bermúdez, Count of Colombi | [15] |
| 1852 | 1854 | José del Castillo y Ayensa | Second term [15] |
| 1854 | 1855 | Miguel de los Santos de Bañuelos y Travel | [15] |
| 1859 | | Antonio de los Ríos y Rosas | [18] |
| 1861 | Manuel Pando Fernández de Pinedo | [19] |
| 1864 | Gerardo de Souza | [15] |
| 1864 | | Joaquín Francisco Pacheco | [20] |
| 1864 | 1866 | Francisco Javier de Istúriz | [15] |
| 1866 | 1867 | Luis José Sartorius y Tapia | [15] |
| 1867 | 1868 | Alejandro de Castro y Casal | [15] |
| 1868 | 1869 | José Posada Herrera | [21] [22] |
| 1870 | 1876 | Viscount of Oña | [15] |
| 1875 | Juan Álvarez de Lorenzana, Viscount of Barrantes | [23] |
| 1875 | 1875 | Antonio Benavides Fernández de Navarrete | [24] [25] |
| 1876 | 1881 | Francisco de Cárdenas | [15] |
| 1881 | 1884 | Alejandro Groizard y Gómez de la Serna | [26] |
| 1884 | 1886 | Mariano Roca de Togores, Marquess of Molins | [27] [28] |
| 1890 | 1890 | Luis Pidal y Mon | [29] |
| 1893 | 1901 | Rafael Carlos Merry del Val | |
| 1901 | 1902 | Alejandro Pidal y Mon | [15] |
| 1902 | 1904 | José Gutiérrez de Agüera | [15] |
| 1904 | 1904 | Luis Polo de Bernabé Pilón | |
| 1904 | 1905 | Manuel Aguirre de Tejada | [15] |
| 1905 | 1906 | Rodrigo de Figueroa y Torres | [15] |
| 1906 | 1911 | Emilio de Ojeda y Perpiñán | |
| 1913 | 1913 | Fermín Calbetón y Blanchon | [30] |
| 1913 | 1916 | Cipriano Muñoz y Manzano, Count of the Viñaza | |
| 1916 | 1917 | Fermín Calbetón y Blanchon | [31] |
| 1922 | 1922 | Wenceslao Ramírez de Villa-Urrutia, 1st Marquis of Villa-Urrutia | |
| 1923 | | Diego Atienza de Reinosa | [32] |
| 1926 | 1930 | Antonio Magaz y Pers, 2nd Marquess of Magaz. | |
| 1930 | 1931 | Emilio de Palacios y Fau | |
| 1931 | 1934 | Eduardo García Comin | [15] |
| 1934 | 1936 | Leandro Pita Romero | |
| 1936 | 1938 | Luis de Zulueta y Escolano | |
| 1938 | 1942 | José de Yanguas Messía | [33] |
| 1942 | 1945 | Domingo de las Bárcenas y Lopez-Mollinedo Mercado | [34] |
| 1946 | 1948 | Pablo de Churruca y Dotres, Marquess of Aycinena | previously Ambassador in Lima [35] |
| 1948 | 1951 | Joaquín Ruiz-Giménez Cortés | |
| 1951 | 1956 | Fernando María Castiella y Maíz | |
| 1957 | 1962 | Francisco Gómez de Llano | [15] |
| 1962 | 1964 | José María Doussinague y Texidor | [15] |
| 1964 | 1972 | Antonio Garrigues Díaz-Cañabate, Marquess of Garrigues. | |
| 1972 | 1973 | Juan Pablo de Lojendio e Irure | [36] |
| 1973 | 1974 | Gabriel Martínez de Mata | [15] |
| 1974 | 1976 | Gabriel Fernández de Valderrama y Moreno | [15] |
| 1976 | 1977 | Gonzalo Fernández de Córdova y Moreno | [15] |
| 1977 | 1980 | Ángel Sanz-Briz | |
| 1980 | 1983 | José Joaquín Puig de la Bellacasa y Urdampilleta | |
| 1983 | 1985 | Nuño Aguirre de Cárcer y López de Sagredo | [37] |
| 1985 | 1987 | Gonzalo Puente Ojea | |
| 1987 | 1992 | Jesús Ezquerra Calvo | |
| 1992 | 1997 | Pedro López de Aguirrebengoa | |
| 1997 | 2004 | Carlos Abella y Ramallo | [38] |
| 2004 | 2006 | Jorge Dezcallar de Mazarredo | |
| 2006 | 2011 | Francisco Vázquez Vázquez | |
| 2011 | 2012 | María Jesús Figa López-Palop | |
| 2012 | 2017 | Eduardo Gutiérrez Sáenz de Buruaga | |
| 2017 | 2018 | Gerardo Ángel Bugallo Ottone | |
| 2018 | 2021 | María del Carmen de la Peña Corcuera | |
| 2022 | Incumbent | María Isabel Celaá Diéguez | |