Heads of Mission
(This list is incomplete)
• 1825–1835: Sir Robert Ker Porter, Consul at Caracas
• 1835–1841: Sir Robert Ker Porter, Chargé D'Affaires and Consul General
• 1841–1843: Sir Daniel Florence O'Leary, Acting Consul General
• February 1858: Sir Philip Edmund Wodehouse, Special Mission to Caracas

Minister Residents to Venezuela
• 1884–1888: Frederic Robert St John
• 1902–1903: Sir Henry Bax-Ironside, Minister Resident

Ambassadors to Venezuela
• 1932–1936: Sir Edward Keeling
• 1936–1939: Sir Ernest Gye
• 1939–1944: Sir Donald Gainer
• 1944–1948: Sir George Ogilve-Forbes
• 1948–1951: Sir John Magowan
• 1951–1955: Sir Robert Urquart
• 1955–1961: Sir John Walker, KCMG, OBE
• 1961–1964: Sir Douglas Laird Busk
• 1964–1969: Sir Anthony Lincoln, KCMG, CVO
• 1969–1973: Sir Donald Hopson, KCMG, DSO, MC, TD
• 1973–1975: Sir Lees Mayall, KCMG, CMG
• 1975–1979: Sir Jock Taylor, KCMG
• 1979–1982: Sir Reginald Secondé, KCMG, CVO
• 1982–1985: Sir Hugh Carless, CMG
• 1985–1988: Michael Newington, CMG
• 1988–1994: Giles Eden Fitzherbert, CMG
• 1994–1997: John G. Flynn, CMG
• 1997–2000: Richard D. Wilkinson, CVO
• 2000–2003: Dr. John E. Hughes
• 2003–2006: Donald Alexander Lamont
• 2007–present: Catherine Jane Royle