Officials from the Office of the Third Sector will meet counterparts at the Department for Work and Pensions to discuss concerns raised by umbrella body Navca over the department's £8m volunteer brokerage scheme.
Kevin Curley, chief executive of Navca, last week asked third sector minister Angela Smith to take up with the DWP his concerns about the treatment of volunteer centres by charities running the scheme.
An OTS spokesman said the two departments worked closely on the scheme and would discuss Navca's concerns.
The scheme, which began in April, was part of the Government's action plan to help the sector through the recession.
It is being led by environmental charity BTCV and has been set up to match 34,000 jobseekers with volunteer placements over the next two years by asking job centre staff to refer them to one of the participating charities, which will in turn find them local placements.
In the letter, Curley says some volunteer centres have been "marginalised or excluded" under the scheme. He says many of the centres have tried to work in partnership with the charities involved but their approaches have been rebuffed.
In some cases, the letter says, volunteer centres were invited to match jobseekers with volunteering placements for sums of money that were "an extremely small proportion of the per capita payment made to the lead bodies".
The letter adds: "I am told that in the most extreme cases the main contractor is seeking to use the expertise, experience and resources of the volunteer centre without compensation for the considerable investment they have made.
"Many of our members are concerned that this will leave no legacy to local people when the scheme ends."
An OTS spokesman said: "The volunteer brokerage programme is a success so far: by the end of October, 2,365 people had completed placements under the scheme. But we will respond to Kevin Curley and we will talk to the DWP about the issues he has raised."