They want schools to pay them pound;1.25 for each overhead projector transparency that a school makes and 25p for every enlargement made of books.
The demand, from the Copyright Licensing Agency, will be on top of the annual fees believed to be up to pound;3.5 million nationally paid to cover photocopying in schools.
David Hart, general secretary of the National Association of Head Teachers, condemned the new fees, which come into effect from April, as "absolutely outrageous".
"There is no justification that schools should have to bear the cost of delivering the national literacy strategy," he said.
Mr Hart said the copyright agency should "not be surprised if schools rise up and object in their thousands to any additional demands on their budgets".
Schools which photocopy materials must hold a copyright licence with the LA which covers books, journals and magazines published in the UK and 17 countries.
Up to the end of March, local authorities have been responsible for licences for schools. This responsibility will be devolved to schools in April.
The Centre for Education Management, which has worked with the CLA for the past decade on behalf of some 1,200 schools, has severed its links following the introduction of the literacy
Adrian Pritchard, managing director, said: "We are saddened to see this approach and wish to have no part in the collection of these fees."
The Local Government Association now wants to broker a meeting between the CLA, teacher unions and councils.
Graham Lane, education chair of the Local Government Association, described the new arrangements as ridiculous and added: "Schools need maximum freedom but they don't want maximum expense."
Schools have to tell the CLA how many copies they have made each term.