Stephen Dunmore will start in the role on 19 September, taking over from Richard Greenhalgh, who has chaired the charity since 2012.
Before joining the regulator, Dunmore was the interim chief executive of the Family and Childcare Trust and had spent a total of 10 years as chief executive of what was then called the Big Lottery Fund and its predecessor the New Opportunities Fund, which merged with the Community Fund in 2003 to create the BLF.
The organisation, which distributes National Lottery funding to good causes, has since changed its name to the National Lottery Community Fund.
In 2008, Dunmore was appointed as an adviser to the Office of the Third Sector, the forerunner to the Office for Civil Society.
He has also held chief executive roles at the infrastructure body Capacitybuilders, the grant-maker The Diana Princess of Wales Memorial Fund and the former regulation body the National Consumer Council, among others.
Dunmore said: "It’s a particular privilege to join a charity with such a rich history in voluntary service and one that is so relevant and needed today.
"I’m passionate about volunteering and believe the work the charity does to support the NHS and older people in the community is vital, particularly given the current pressure on public services."
Catherine Johnstone, chief executive of the Royal Voluntary Service, said Dunmore’s "skills and diverse experience, combined with his outstanding record of strategic leadership, will be integral to helping us realise our ambitious plans for volunteering in Britain, and we are all looking forward to working with him".
Dunmore is also chair of the grant-making committee for The Prince’s Countryside Fund and council member and treasurer of the Society of Antiquaries, which he will combine with his new role at the RVS, according to an RVS statement.