The schools will be able to apply to the books chain for a selection of fiction from a list drawn up by the Department for Education and Employment. The list includes a wide range of authors including children's favourites Roald Dahl and Michael Rosen. The Welsh, Scottish and Northern Ireland Offices were also consulted.
The DFEE has chosen the 400 schools from those participating in the National Literacy Project.
David Blunkett, Education and Employment Secretary, said: "This initiative from WH Smith is a significant contribution to the Government's campaign to raise literacy standards. It is an excellent example of how this Government and business can work together and I am confident that it will help fulfil the target for literacy in the years to come."
Jeremy Hardie, chairman of WH Smith, said the Pounds 1.5 million scheme will put half a million books into the hands of 75,000 children.
A spokeswoman for the company said: "These will be new, additional books. The scheme is not replacing state funding - there is no funding for books."
Anne Barnes, general secretary of the National Association for the Teaching of English,said: "It is a wonderful mix I it is a pity that all schools cannot have the opportunity of having new reading books."
The scheme was given a qualified welcome by the Association of Teachers and Lecturers. A spokesman said: "It is a pity that successive cuts mean schools do not have enough books and materials."