The move will form part of an expansion to the existing Train to Gain scheme, which was launched this week by John Denham, minister for innovation, universities and skills. The initiative helps businesses assess their skills and recommends training. It was previously open only to paid staff in the sector.
Phil Hope, Minister for the Third Sector, said: "In extending Train to Gain to volunteers, we are giving new opportunities to thousands of people to gain skills."
By 2010, more than 500,000 people in total are expected to have achieved a level 2 qualification through the scheme, which is equivalent to five GCSEs.