V received all of the funding for its vschools programme, under which schools were allowed to make community work part of their curricula, from the Department for Education. The programme was launched in January, with one-year government funding worth £8m.
The 90 staff include school advisers who were auditing existing community schemes at schools and offering suggestions for new volunteering projects.
Jayne Colquhoun, corporate affairs director at v, said it was "complete folly" to close the vschools programme.
"The government wants to set up a National Citizen Service scheme, and this programme was preparing young people for that," she said.
Colquhoun said v was told yesterday that the scheme would be abolished and had launched a consultation with its staff about the redundancies.
In a statement, Terry Ryall, chief executive of v, said: "The decision not to fund vschools is a big blow for the big society. This government, like all others, will be judged by its actions rather than its words.
"In just four months vschools has established a universal volunteering and social action initiative for every state secondary school in England. Feedback from schools and local government has been universally positive and welcoming."
The statement said savings to the public purse as a result of scrapping the scheme would be minimal, because the start-up funding had already been spent.
A statement from the Department for Education said: "The action needed this year to address the deficit is unprecedented. The government is still fully committed to youth volunteering. Young people of all ages can and do already volunteer, with their families, at school and in the wider community.
"The National Citizen Service programme will act as a gateway to the big society for many young people."