Ms Mone, brought up in Glasgow's East End, founded lingerie firm Ultimo in her 20s, after leaving school at 15.
She sold an 80% stake in the firm last year in a multi-million pound deal.
The review will look to identify obstacles to people in deprived areas starting new businesses.
"Entrepreneurship can play an important role in supporting economic growth and creating jobs in our most disadvantaged communities," said Work and Pensions Secretary Iain Duncan Smith.
"However, people living in those areas face a range of additional barriers they need to overcome in starting and growing businesses."
The government said these barriers included a lack of business and social networks, and a lack of inspiring role models.
It asked Ms Mone to draw on her own experiences, which included leaving school with no qualifications and having a child at 18.
"It's an honour to be appointed to lead this review because I know how tough it can be setting up successful businesses," she said.
"My philosophy is that it does not matter where you are from, what education you have, or if you are from an affluent background or not, you can make it if you work hard, set your goals and never give up."
Ms Mone co-founded the original Ultimo parent company MJM International with her ex-husband Michael in 1996, and created brands including Ultimo Miracle Shapewear and Miss Ultimo.
She was awarded an OBE in 2010.
Scottish entrepreneur Michelle Mone has been appointed by the government to carry out a review into how best to encourage start-ups in areas of high unemployment.