Matt Hyde will take over on 29 April next year from current chief executive Derek Twine, who has spent 16 years at the helm.
Hyde has been chief executive of the NUS since 2006, overseeing the organisation against the backdrop of rising tuition fees and student demonstrations.
Hyde, who was himself a Cub Scout and later a Scout, said it is an “exciting time” for the movement.
“The Scout movement plays a vital role transforming the lives of young people across the UK and I believe my leadership, skills and experience will help the Scout Association to achieve its 2018 vision to make a real social impact on the communities which we serve,” he said.
“Preparing young people to be active citizens across all the diverse communities which scouting serves is essential to ensure that we continue to meet the needs of young people in the 21st century.
“I am passionate about the power of informal learning and I am planning to build on the great work of my predecessor Derek Twine.”
The Scouts have enjoyed increasing popularity in recent years, with overall membership now topping 525,000, after year-on-year increases since 2005.
However, the movement’s waiting list currently extends to 36,000 young people, largely due to a well-documented shortage of adult volunteers – with some 7,000 more needed.
Scout Association chairman Sir Alan Craft said Hyde would “bring a great deal of experience” to the role and was impressed by his “enthusiasm and passion” for scouting.
“As our membership continues to grow, the movement is looking forward to an exciting future and we are confident that he will play a key role in helping us to achieve that,” Craft said.