The show follows on from the duo's earlier TV series The Mitchell and Webb Situation, and is an extension of their Radio 4 sketch show That Mitchell and Webb Sound. The show's producer Gareth Edwards commented that the show's pitch to the BBC "was the shortest pitch I've ever written", citing that the show "has worked on the radio, just like Little Britain worked on the radio and Dead Ringers worked on the radio, and they transferred successfully to TV, so why don't you [the BBC] transfer this one to TV as well?"
A pilot for the show was filmed on 27 January 2006 at BBC Television Centre, with a full series being later commissioned. Preview nights for the show were held at The Drill Hall in London on 11 January and 20 March 2006, and at Ginglik in Shepherd's Bush in London on 14 and 21 May 2006. These took the form of a radio recording, with verbal prompting to the audience for any visual element that would be required. The series was shot on location in June 2006 and three audience recording sessions were held in Studio 4 at BBC Television Centre on 14, 21 and 28 July 2006.
Following the first series, the pair went on a tour of forty-four UK venues between October and December 2006, entitled The Two Faces of Mitchell and Webb, featuring many of the same sketches as That Mitchell and Webb Look.
A preview night for the second series was held on 18 May 2007 at The Drill Hall in London. This series was shot in high-definition on location during June/July 2007 and three studio recordings with an audience were held at TC8 in Television Centre on 3 August, 10 August and 17 August 2007.
Two preview nights for series three were announced on 30 June 2008 on the BBC Tickets website; all tickets were booked in less than 24 hours. The first preview night took place on 13 July 2008 at The Drill Hall, with the second held there on 10 August, 2008. Two audience recording sessions at Television Centre — with additional live sketches — were announced on 3 October 2008, and took place on 31 October and 7 November 2008, again in high-definition in studio TC8. A third recording session at the BBC Radio Theatre was announced on 10 October 2008, taking place on 18 November 2008.
A preview night for the fourth series was announced on 18 November 2009 on the BBC Tickets website; this was held on 26 November 2009 at The Drill Hall. David Mitchell confirmed via Twitter that the fourth series was being filmed, and an article in the Radio Times confirmed that the new series would begin July 13, 2010.
The show was nominated for two British Comedy Awards in 2006, in the categories of "Britain's Best New TV Comedy" and the "Highland Spring People's Choice", it won neither of the awards. However, the show did go on to receive a BAFTA in 2007, in the category "Best comedy programme or series" and been named "Best British TV Sketch Show 2006" in The Comedy.co.uk Awards
- The first series was released on DVD in the UK by Contender Home Video on 29 October 2007.
- The second series was released on DVD in the UK by Fremantle Media on 20 October 2008.
- The third series was released on DVD in the UK by 2|entertain on 20 July 2009.