Steve Holliday, who until last July was chief executive of National Grid, will lead the government's youth full-time social action review.
The independent review will look at the challenges and benefits of young people committing to full-time social action - classed as more than 16 hours per week for at least six months.
Holliday is expected to report to ministers in October after investigating barriers youth organisations face in running long-term volunteering initiatives as well as identifying ways to encourage young people to take part.
During his time at National Grid Holliday also worked with City Year UK, the youth and education charity supported by the utilities firm that offers full-time voluntary roles to young people in schools through a model originated in the United States.
Holliday said: "I've seen youth social action benefit the development and character in young people, giving them employability skills while making a real difference in their communities.
"The challenge is to see how can we expand full-time volunteering as a real option for young people."
His appointment has been welcomed by City Year chief executive Sophie Livingstone.
"He has been a strong supporter of young people making a difference through full-time social action and it is a fantastic statement of intent from the government to confirm such a respected business figure in this role," she said.
Youth minister Rob Wilson, who launched the review last December, added: "Steve's experience, accompanied by an understanding of the youth sector and the importance of volunteering, made him a great fit for the role."
An announcement of membership of the review's advisory board will be made at a later date. This is expected to include both voluntary and private sector representatives.
