| Rt Hon Sir Henry John Temple, Viscount Palmerston | 19 February 1858 | 11 June 1859 |
| Rt Hon Sir William George Granville Venables Vernon-Harcourt | October 1896 | December 1898 |
| Sir Henry Campbell-Bannerman | 6 February 1899 | 5 December 1905 |
| Rt Hon Arthur James Balfour | 5 December 1905 | 13 November 1911 |
| Rt Hon Andrew Bonar Law | 13 November 1911 | 15 May 1915 |
| Rt Hon Sir Edward Henry Carson | 19 October 1915 | 6 December 1916 |
| Rt Hon Henry Herbert Asquith | 6 December 1916 | 3 February 1919 |
| Rt Hon Sir Donald Maclean | 3 February 1919 | 12 February 1920 |
| Rt Hon Henry Herbert Asquith | 1920 | 21 November 1922 |
| James Ramsay MacDonald | 21 November 1922 | 22 January 1924 |
| Rt Hon Stanley Baldwin | 22 January 1924 | 4 November 1924 |
| Rt Hon James Ramsay MacDonald | 4 November 1924 | 8 June 1929 |
| Rt Hon Stanley Baldwin | 8 June 1929 | 24 August 1931 |
| Rt Hon Arthur Henderson | 24 August 1931 | November 1931 |
| Rt Hon George Lansbury | November 1931 | 25 October 1935 |
| Rt Hon Clement Richard Attlee | 8 October 1935 | 22 May 1940 |
| Rt Hon Hastings Bertrand Lees-Smith | 22 May 1940 | 21 January 1942 |
| Rt Hon Arthur Greenwood | February 1942 | 23 May 1945 |
| Rt Hon Clement Richard Attlee | 23 May 1945 | 26 July 1945 |
| Rt Hon Winston Leonard Spencer Churchill | 26 July 1945 | 26 October 1951 |
| Rt Hon Clement Richard Attlee | 26 October 1951 | 14 December 1955 |
| Rt Hon Hugh Todd Naylor Gaitskell | 14 December 1955 | 18 January 1963 |
| Rt Hon James Harold Wilson | 14 February 1963 | 16 October 1964 |
| Rt Hon Sir Alexander Frederick Douglas-Home | 16 October 1964 | 27 July 1965 |
| Rt Hon Edward Richard George Heath | 27 July 1965 | 19 June 1970 |
| Rt Hon James Harold Wilson | 19 June 1970 | 4 March 1974 |
| Rt Hon Edward Richard George Heath | 4 March 1974 | 11 February 1975 |
| Rt Hon Margaret Hilda Thatcher | 11 February 1975 | 4 May 1979 |
| Rt Hon Leonard James Callaghan | 4 May 1979 | 3 November 1980 |
| Rt Hon Michael Mackintosh Foot | 3 November 1980 | 2 October 1983 |
| Rt Hon Neil Gordon Kinnock | 2 October 1983 | 18 July 1992 |
| Rt Hon John Smith | 18 July 1992 | 12 May 1994 |
| Rt Hon Margaret Mary Beckett | 12 May 1994 | 12 July 1994 |
| Anthony Charles Lynton Blair | 21 July 1994 | 2 May 1997 |
| Rt Hon John Roy Major | 2 May 1997 | 19 June 1997 |
| Rt Hon William Jefferson Hague | 19 June 1997 | 13 September 2001 |
| George Iain Duncan Smith | 13 September 2001 | 6 November 2003 |
| Rt Hon Michael Howard | 6 November 2003 | 6 December 2005 |
| David William Donald Cameron | 6 December 2005 | 11 May 2010 |
| Rt Hon Harriet Ruth Harman | 11 May 2010 | 25 September 2010 |
| Rt Hon Edward Samuel Miliband | 25 September 2010 | 8 May 2015 |
| Rt Hon Harriet Ruth Harman | 8 May 2015 | 12 September 2015 |
| Jeremy Bernard Corbyn | 12 September 2015 | 4 April 2020 |
| Rt Hon Sir Keir Rodney Starmer | 4 April 2020 | 5 July 2024 |