Nick Clegg is to throw his weight behind an initiative to send employees into state schools to talk about their careers.
The Education and Employers Taskforce, the charity behind the plan, wants to sign up more than 100,000 voluntary speakers who can inspire youngsters about the possibilities open to them.
The scheme, called Inspiring the Future, is meant to give state school pupils access to the kind of careers advice and first-hand accounts that many private schools offer.
Research by the Education and Employers Taskforce suggests 80% of independent schools regularly have external speakers to talk to pupils about career options.
The idea is strongly supported by the Deputy Prime Minister, who is driving efforts within the coalition Government to improve social mobility and ensure poorer youngsters are not hindered in life because of their background.
Other figures supporting the scheme include Apprentice star and entrepreneur Karren Brady, actress Joanna Lumley and the head chef of The Ivy restaurant, Gary Lee.
Mr Clegg said: "Too many young people get the message that the best jobs are not for them.
"Inspiring the Future will give state school students the chance to see, hear and make a connection with someone in a career or job they might not have thought about.
"Today we're calling on doctors, nurses, lawyers, builders, business people, civil servants, farmers, mechanics, engineers and other working people to give up just an hour of their time to talk to students in their local state school about how they got where they are today.
"The power of making connections that inspire young people is immeasurable and can be life-changing.
"Many successful people can point to a moment in their lives when they were inspired to become the people they are today. Now it's their turn to help young people fulfil their potential."
Sir Roger Carr, president of employers' organisation the CBI, said: "There is nothing more compelling for young people thinking about their future careers than meeting and speaking to inspirational people who do the jobs they are considering. That is why the CBI is pleased to support Inspiring the Future.
"We desperately need to tackle the corrosive effects of high youth unemployment in the UK, so I would urge employers to sign up to this initiative and encourage their staff to get involved and provide valuable insights into their careers."
Brian Lightman, president of the Association of School and College Leaders which represents 17,000 school leaders, said: "The world of work offers a bewildering range of opportunities for young people. It is immensely important that they have the chance to gain insights early on about different jobs and careers, especially when they cover areas outside their immediate experience."