* [[Martin Earwicker]] (2001–06): Chief Executive from its creation in 2001, until he left in 2006 for the [[Science Museum, London|Science Museum]].<ref>{{cite news |last1=Smith |first1=Michael |title=Wanted: gadget wizard to replace the real life Q |url=https://www.thetimes.co.uk/article/wanted-gadget-wizard-to-replace-the-real-life-q-8zm9v63rgt2 |access-date=10 September 2020 |work=The Times |date=16 July 2006}}</ref>
* Dr [[Frances Saunders (scientist)|Frances Saunders]] (2006–11): took over as acting Chief Executive in May 2006<ref>{{cite web |url=http://www.parliament.the-stationery-office.co.uk/pa/cm200607/cmselect/cmdfence/84/6112802.htm |title=House of Commons – Defence – Minutes of Evidence |year=2011 |work=parliament.the-stationery-office.co.uk |archive-url=https://web.archive.org/web/20120829024416/http://www.parliament.the-stationery-office.co.uk/pa/cm200607/cmselect/cmdfence/84/6112802.htm|archive-date=29 August 2012 |url-status=dead |access-date=12 June 2011}}</ref> and was appointed as Chief Executive in August 2007.<ref>{{cite web |url=http://www.dstl.gov.uk/downloads/15-08-07.pdf |title=Press release: Heading up Defence Science – New Chief Executive appointed at Dstl |date=16 August 2007 |website=dstl.gov.uk |archive-url=https://web.archive.org/web/20110928062654/http://www.dstl.gov.uk/downloads/15-08-07.pdf |archive-date=28 September 2011 }}</ref><ref>{{cite news |url=https://www.theguardian.com/education/2007/nov/20/highereducationprofile.academicexperts |title=Interview: Frances Saunders | Education | The Guardian |last=Gilbert |first=Natasha |date=20 November 2007 |work=[[The Guardian]] |access-date=12 June 2011 |___location=London |issn=0261-3077 |oclc=60623878}}</ref> On 29 June 2011, Saunders announced to staff that her post had been advertised and that she would not be applying.<ref>Global email to all staff dated 29/6/11</ref>
* [[Jonathan Lyle]] (2012–17): formerly Director of the Programme Office at Dstl, placed into an acting role and was appointed in March 2012.<ref>{{cite news |url=https://www.gov.uk/government/news/jonathan-lyle-named-as-new-dstl-chief-executive |title=Jonathan Lyle named as new Dstl Chief Executive |access-date=16 February 2014 |publisher=[[Government of the United Kingdom|GOV.UK]]}}</ref>
* David Marsh: acting Chief Executive from September 2017 to January 2018.<ref name=":0" />
