| Appointed/accreditation | Incumbent | Monarch | Envoy to | Left office |
| 1505 | John Stile | Henry VIII of England | Ferdinand II of Aragon | 16 June 1518 |
| 3 June 1512 | William Knight | Henry VIII of England | Ferdinand II of Aragon | 1 September 1513 |
| 15 July 1517 | Sir Thomas Spinelly | Henry VIII of England | Charles I of Spain | 1522 |
| 28 February 1518 | John Kite John Bourchier, 2nd Baron Berners | Henry VIII of England | Charles I of Spain | 1 March 1519 |
| 1533 | Richard Pate | Henry VIII of England | Charles I of Spain | 1537 |
| 1537 | Sir Thomas Wyatt | Henry VIII of England | Charles I of Spain | 1539 |
| 12 March 1554 | John Russell, 1st Earl of Bedford Thomas Radclyffe, 3rd Earl of Sussex | Mary I of England | Philip II of Spain | 20 July 1554 |
| 12 January 1560 | Anthony Browne, 1st Viscount Montagu | Elizabeth I of England | Philip II of Spain | 24 June 1560 |
| 24 June 1560 | Anthony Browne, 1st Viscount Montagu Sir Thomas Chamberlain | Elizabeth I of England | Philip II of Spain | 24 June 1562 |
| 30 September 1561 | Thomas Chaloner | Elizabeth I of England | Philip II of Spain | 15 May 1565 |
| 5 March 1565 | William Phayre | Elizabeth I of England | Philip II of Spain | 4 April 1566 |
| 12 January 1566 | John Man | Elizabeth I of England | Philip II of Spain | 5 October 1568 |
| 18 November 1576 | Sir John Smith | Elizabeth I of England | Philip II of Spain | 28 July 1577 |
| December 1577 | Thomas Wilkes | Elizabeth I of England | Philip II of Spain | February 1578 |
| May 1579 | Edward Wotton, 1st Baron Wotton | Elizabeth I of England | Philip II of Spain | |
| January 1583 | William Wade | Elizabeth I of England | Philip II of Spain | August 1584 |
| 1584 | Thomas Wilson | Elizabeth I of England | Philip II of Spain | |
| 2 March 1605 | Charles Howard, 1st Earl of Nottingham | James VI and I | Philip III of Spain | 4 July 1577 |
| 1605 | Francis Cottington, 1st Baron Cottington | James VI and I | Philip III of Spain | |
| 1605 | Charles Cornwallis | James VI and I | Philip III of Spain | 1609 |
| 1608 | John Digby, 1st Earl of Bristol | James VI and I | Philip III of Spain | |
| 1609 | Francis Cottington, 1st Baron Cottington | James VI and I | Philip III of Spain | 1611 |
| 1609 | Peter Wyche | James VI and I | Philip IV of Spain | 1611 |
| 1616 | William Cecil, 17th Baron de Ros | James VI and I | Philip III of Spain | |
| 1617 | John Digby, 1st Earl of Bristol | James VI and I | Philip IV of Spain | 1618 |
| 1617 | John Digby, 1st Earl of Bristol | James VI and I | Philip III of Spain | |
| 1618 | Walter Aston, 1st Lord Aston of Forfar | James VI and I | Philip III of Spain | |
| 1622 | Mr. Hole | James VI and I | Philip IV of Spain | |
| 1622 | Simon Digby (fl. 1620–1640s) | James VI and I | Philip IV of Spain | 1640 |
| 1622 | John Digby, 1st Earl of Bristol | James VI and I | Philip IV of Spain | |
| 1623 | Endymion Porter | James VI and I | Philip IV of Spain | |
| 1624 | Stephen Gardiner | James VI and I | Philip IV of Spain | |
| 1 March 1625 | Peter Wyche | Charles I of England | Philip IV of Spain | 30 April 1626 |
| 11 August 1628 | Endymion Porter | Charles I of England | Philip IV of Spain | 5 January 1629 |
| 1 July 1629 | Francis Cottington, 1st Baron Cottington | Charles I of England | Philip IV of Spain | 20 April 1631 |
| 18 December 1630 | Arthur Hopton | Charles I of England | Philip IV of Spain | 23 April 1636 |
| 13 July 1634 | John Taylor | Charles I of England | Philip IV of Spain | 24 May 1635 |
| 26 December 1634 | Walter Aston, 1st Lord Aston of Forfar | Charles I of England | Philip IV of Spain | 31 July 1638 |
| April 1638 | Sir Richard Fanshawe, 1st Baronet | Charles I of England | Philip IV of Spain | 10 June 1638 |
| 21 March 1638 | Arthur Hopton | Charles I of England | Philip IV of Spain | December 1645 |
| 25 January 1650 | Anthony Ascham | English Council of State | Philip IV of Spain | 27 May 1650 |
| 27 May 1650 | George Fisher | English Council of State | Philip IV of Spain | 26 September 1651 |
| 1654 | Anglo-Spanish War (1654-1660) | English Council of State | Philip IV of Spain | 1660 |
| 20 February 1666 | Edward Montagu, 1st Earl of Sandwich | Charles II of England | Charles II of Spain | 11 October 1668 |
| 26 February 1666 | Robert Southwell | Charles II of England | Charles II of Spain | 22 June 1666 |
| 10 July 1668 | Sir John Werden, 1st Baronet | Charles II of England | Charles II of Spain | 10 June 1668 |
| 10 July 1668 | William Godolphin | Charles II of England | Charles II of Spain | 10 June 1668 |
| 21 November 1671 | Robert Spencer, 2nd Earl of Sunderland | Charles II of England | Charles II of Spain | 20 May 1672 |
| 29 June 1677 | Ignatius White | Charles II of England | Charles II of Spain | October 1677 |
| 12 June 1679 | Sir Henry Goodricke, 2nd Baronet | Charles II of England | Charles II of Spain | 27 March 1683 |
| 10 December 1682 | Peter Lefett | Charles II of England | Charles II of Spain | 16 November 1685 |
| 13 May 1685 | Charles Granville, 2nd Earl of Bath | Charles II of England | Charles II of Spain | December 1688 |
| 13 May 1685 | John Stafford | James II of England | Charles II of Spain | December 1688 |
| May 1689 | Viscount Dursley | Mary II of England | Charles II of Spain | August 1689 |
| 1689 | Alexander Stanhope | Mary II of England | Charles II of Spain | 1699 |
| 1699 | Francis Schonenberg | William III of England | Charles II of Spain | 1702 |
| 1702 | War of the Spanish Succession | William III of England | Philip V of Spain | 1702 |
| 1705 | Mitford Crowe | Anne, Queen of Great Britain | Philip V of Spain | 1706 |
| 1705 | Paul Methuen | Anne, Queen of Great Britain | Philip V of Spain | 1706 |
| 1706 | Charles Mordaunt, 3rd Earl of Peterborough, James Stanhope, 1st Earl Stanhope | Anne, Queen of Great Britain | Charles III of Hungary |
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