The first schools to come forward are expected to go out to bid on April 2 next year.
PFI contracts for 27 years are expected to include firm provisions for apprenticeship training during construction.
Preliminary details for the officially estimated £1bn-£3bn programme were published today in the Official Journal of the European Union.
The Government said the programme would cover the equivalent of building or rebuilding approximately 100 secondary schools, although the full scale of the programme is yet to be finalised.
When additional primary schools, special schools, sixth form colleges and alternative provision are also included, it expects up to 300 schools projects to be built using PFI.
Around 20% of the total programme is pencilled to be delivered each year, with the first schools scheduled to open in the academic year of 2014-15.
The contracts to design, build, operate and maintain will include hard and soft facilities management for 27 years.
The Government said it wanted to encourage potential bidders to join an early market engagement exercise to inform the procurement plan ahead of bidding.
Interested firms can contact Bryony Mines at Partnerships for Schools by calling 02033017000 or on email: firstname.lastname@example.org