All civil servants will be encouraged to do at least one day of volunteering a year under plans announced yesterday.
The government hopes the move will result in the civil service providing 30,000 volunteering days a year.
Charities will be able to request help from the civil service when they need it.
Senior civil servants will be expected to encourage their colleagues to volunteer and "encouraging volunteering" will feature in annual appraisals for senior managers.
The businesses Shell, BT and KPMG have decided to match the volunteering policy.
Nick Hurd, the Minister for Civil Society, said the scheme was "about setting a lead. It is in the interests of every organisation to develop the skills of their people."
Justin Davis Smith, chief executive of Volunteering England, welcomed the scheme and the involvement of major companies. "There is huge scope for collaboration across sectors in opening up volunteering opportunities, for sharing skills and enjoying different ways of working," he said.
A spokesman for the Cabinet Office said the new policy would begin in April.