| Name |
Term |
Nominated by |
Appointed by |
Accredited to |
| 1 |
Fermín Sanz-Orrio |
26 January 1952[5] – 5 May 1954 (2 years, 99 days) |
Alberto Martín-Artajo |
Francisco Franco |
Malik Ghulam Muhammad |
| 2 |
Francisco de Amat y Torres |
1 June 1954[6] – 22 June 1955 (1 year, 21 days) |
| 3 |
Manuel Galán Pacheco de Padilla [es][b] |
25 June 1955[7] – 15 January 1958 (2 years, 204 days) |
Iskander Mirza |
| 4 |
Fernando Canthal y Girón [es] |
15 January 1958[8] – 25 August 1958 (222 days) |
Fernando María Castiella |
Iskander Mirza |
| 5 |
Pedro Seoane y Diana Marquess of Orellana la Vieja |
25 August 1958[9] – 6 March 1967 (8 years, 193 days) |
| 6 |
Eduardo Gasset y Díez de Ulzurrun Count of Peñarrubias |
20 March 1967[10] – 4 April 1970 (3 years, 15 days) |
Ayub Khan |
| 7 |
Manuel de la Calzada Herranz Marquess of Santa Cruz de Inguanzo |
27 June 1970[11] – 18 March 1972 (1 year, 265 days) |
Gregorio López-Bravo |
Yahya Khan |
| 8 |
Marcelino Fernández Díez |
18 March 1972[12] – 25 March 1976 (4 years, 7 days) |
Zulfikar Ali Bhutto |
| 9 |
Ignacio de Casso García |
20 May 1976[13] – 29 July 1981 (5 years, 70 days) |
The Count of Motrico |
Juan Carlos I |
Fazal Ilahi Chaudhry |
| 10 |
Víctor Sánchez-Mesas y Juste |
29 July 1981[14] – 8 October 1984 (3 years, 71 days) |
José Pedro Pérez-Llorca |
Muhammad Zia-ul-Haq |
| 11 |
José María Campoamor Elías |
8 October 1984[15] – 28 July 1986 (1 year, 293 days) |
Fernando Morán |
| 12 |
José García Bañón [es] |
28 July 1986[16] – 22 June 1991 (4 years, 329 days) |
Francisco Fernández Ordóñez |
| 13 |
José María Ullrich Rojas [es] |
4 September 1991[17] – 12 March 1994 (5 years, 219 days) |
Ghulam Ishaq Khan |
| 14 |
Lorenzo González Alonso |
26 March 1994[18] – 26 February 1998 (3 years, 337 days) |
Javier Solana |
Farooq Leghari |
| 15 |
Aurora Bernáldez [es] |
26 February 1998[19] – 3 January 2002 (3 years, 311 days) |
Abel Matutes |
Muhammad Rafiq Tarar |
| 16 |
Antonio Segura Morís[c] |
3 January 2002[20] – 1 February 2005 (3 years, 1 day) |
Josep Piqué |
Pervez Musharraf |
| 17 |
José María Robles Fraga |
1 February 2005[21] – 23 December 2008 (3 years, 326 days) |
Miguel Ángel Moratinos |
| 18 |
Gonzalo María Quintero [es] |
23 December 2008[22] – 26 May 2012[23] (3 years, 155 days) |
Asif Ali Zardari |
| 19 |
Javier María Carbajosa Sánchez [es] |
26 May 2012[24] – 13 June 2015 (3 years, 18 days) |
José Manuel García-Margallo |
| 20 |
Carlos César Morales Sánchez |
13 June 2015[25] – 12 October 2018 (3 years, 121 days) |
Felipe VI |
Mamnoon Hussain |
| 21 |
Manuel Durán Giménez-Rico [es] |
12 October 2018[26] – 15 June 2022 (3 years, 246 days) |
Josep Borrell |
Arif Alvi |
| 22 |
José Antonio de Ory Peral [es] |
15 June 2022[27] – present (3 years, 150 days) |
José Manuel Albares |