The Prince's Trust will hire 100 "job ambassadors" to help find jobs for a further 100,000 long-term unemployed.
The new scheme will see young people who have been helped by the Prince's Trust mentoring other jobless youngsters.
The trust said it was responding to staggering levels of youth unemployment levels, which hit 1.04 million in January.
Prince Charles will visit the London headquarters of his youth charity to make the announcement.
"We know that long-term unemployment can be demoralising - crushing self-esteem and derailing ambition. The young people we are employing will have lived through this. They will be able to share their own experiences with today's unemployed young people and - crucially - give them the inspiration, advice and guidance they need to find a job," Martina Milburn, chief executive said.
The trust was developed to provide practical and financial support, develop key workplace skills such as confidence and, in general, provide motivation to young people. Since 1976, the Trust has assisted over 600,000 young people.
"This scheme will make sure an unemployed generation does not become an unemployable one," Milburn added.
The Job Ambassador initiative will launch in the West Midlands, where Wolverhampton has one of the highest youth unemployment rates.
It will then be rolled out across the country, focusing on other unemployment hotspots, particularly helping the long-term unemployed.