He will take over from Stephen Henwood who is stepping down from the role after nine years.
Smith will assume responsibility for the operation, decommissioning and clean-up of 17 legacy nuclear sites, including Sellafield.
“I am honoured to have been asked by the government to become the NDA’s Chairman and in doing so oversee the important task of decommissioning the UK’s nuclear legacy,” he said.
“It is a privilege to be taking up this post with the NDA, which through a highly-skilled workforce, cutting-edge innovation, and strong utilisation of the UK supply chain, is making good progress on delivering its exceptionally challenging mission.”
Smith has been a non-executive director of the NDA since 2013, serving as a member of its Audit and Risk Assurance Committee. He is currently also a non-executive director at both the Highways Agency and Highways England and the chairman of Angel Trains Group.
After reading chemistry at the University of Oxford, he started his career in the Diplomatic Service, working in London, Hong Kong and Beijing, and was part of the team that negotiated the treaty returning Hong Kong to China.
He spent ten years at the Go-Ahead Group, becoming the managing director for rail development, and was chairman of the Association of Train Operating Companies from 2009 to 2013.
Outgoing energy minister Baroness Neville-Rolfe said: “I would like to thank Stephen Henwood for his hard work and dedication in successfully steering the NDA through a number of complex challenges.
“He hands the mantle to an excellent successor, Tom Smith, who has the experience and knowledge to take the authority forward successfully and to progress the safe decommissioning of the UK’s nuclear legacy.”
Smith’s tenure will run from 1 March 2017 to 29 February 2020.