More than 30,000 heads and deputies have been put on standby to help rebuild the shattered education system in areas of southern Asia hit by the tsunami.
Members of the National Association of Head Teachers have promised to make equipment, staff and expertise available to aid agencies for the next five years.
Charities working in the disaster zone will be able to apply for help through government departments. Schools across Britain will then be alerted to their needs and will be ready to help at short notice with everything from teacher training to technology.
Alan Stockley, headteacher of Landywood school in Walsall and chairman of the NAHT's international committee, said: "It is a hand of friendship. Some schools have lost all their teachers.
"But this will not be a lot of people sitting in comfortable England and deciding what people need: that's no good. It will be the agencies on the ground."
His 400-pupil primary raised pound;7,600 for the disaster victims, while the largest fundraising event, School Aid UK, has now collected Pounds 1,140,603.
But the new initiative is intended to be a long-term commitment, providing practical support to back up the cash.
"Schools have done a tremendous job. I don't know if we will ever know how much they have all raised," said Mr Stockley.
"But there is going to be a need for sustained support over a number of years. People are already forgetting about the tsunami."
Schools were devastated and thousands of teachers killed when the giant wave brought destruction to the coastline of the Indian Ocean on Boxing Day.
In Aceh, one of the worst-hit Indonesian provinces, about 1,000 schools were destroyed and 1,750 teachers killed, leaving 180,000 children without an education.
More than a quarter of a million people are believed to have died in the disaster. Three British teachers were among the missing, while a teaching assistant was also confirmed dead in Thailand.
Jane Moyo, spokeswoman for development agency Action Aid, said: "It is a great initiative, particularly as they are showing such a long-term commitment.
"In an emergency it is the poorest who suffer most. We know there has been a lot of trauma, and for children to get back into a routine and into education is the best treatment. Any offer of professional help is always a welcome opportunity for charities."