| Rt Hon James Griffiths | 18 October 1964 | 5 April 1966 |
| Rt Hon Cledwyn Hughes | April 1966 | April 1968 |
| Thomas George Thomas | 6 April 1968 | 19 June 1970 |
| Rt Hon Peter John Mitchell Thomas | June 1970 | March 1974 |
| Rt Hon John Morris, Baron Morris of Aberavon | March 1974 | May 1979 |
| Roger Nicholas Edwards | May 1979 | 13 June 1987 |
| Rt Hon Peter Edward Walker | 13 June 1987 | May 1990 |
| David James Fletcher Hunt | May 1990 | 27 May 1993 |
| John Alan Redwood | May 1993 | 26 June 1995 |
| William Jefferson Hague | 5 July 1995 | 2 May 1997 |
| Rt Hon Ronald Davies | 3 May 1997 | 27 October 1998 |
| Rt Hon Alun Edward Michael | 27 October 1998 | 28 July 1999 |
| Rt Hon Paul Peter Murphy | 28 July 1999 | 24 October 2002 |
| Rt Hon Peter Gerald Hain | 24 October 2002 | 24 January 2008 |
| Rt Hon Peter Gerald Hain | 5 June 2009 | 11 May 2010 |
| Cheryl Elise Kendall Gillan | 12 May 2010 | 4 September 2012 |
| David Ian Jones | 4 September 2012 | 14 July 2014 |
| Stephen Crabb | 15 July 2014 | 19 March 2016 |
| Alun Hugh Cairns | 19 March 2016 | 6 November 2019 |
| Simon Anthony Hart | 16 December 2019 | 6 July 2022 |
| Rt Hon Robert James Buckland | 7 July 2022 | 25 October 2022 |
| David Thomas Charles Davies | 25 October 2022 |