Heads appointed to jobs paying more than pound;150,000 a year will have their salaries published as part of a government drive to rein in high public sector pay.
School governors will have to write an open letter to Ed Balls, Schools Secretary, justifying their decision if they decide to break the pay threshold in future.
It will be the first time that the highest paid school leaders will be identified and their salaries put into the public domain.
John Dunford, general secretary of the Association of School and College Leaders (ASCL), said keeping public salaries secret was not acceptable. But he described the decision to involve the secretary of state as "centralisation gone mad".
"These salary decisions are made by the governing bodies. I can see no reason why they should need to refer these decisions upwards," he said. "Governing bodies do not pay headteachers more than they need to recruit, retain and reward them."
The move on pay comes as school budgets are put under increasing pressure, despite a pledge made by Chancellor Alistair Darling last week that the education budget will increase in real terms over the next three years.
It follows a speech by Gordon Brown in which the Prime Minister criticised a "culture of excess" in parts of the public sector and said that certain salaries had "lost touch" with people's lives.
Increasing numbers of heads are believed to be receiving salaries in excess of leadership pay scales, which stop at pound;109,658 for a headteacher in inner London. Governing bodies are free to pay more if they consider it necessary to recruit or retain school leaders.
According to the Department for Children, Schools and Families, 220 heads were earning more than pound;100,000 two years ago. Its figures suggest that fewer than 10 heads had salaries in excess of pound;150,000 at that time.
But academies, which are free to operate outside national pay scales, have driven up heads' pay with six-figure salaries and performance bonuses commonplace, even outside of London.
Heads' pay has also risen with the growth in the number of executive headships and school federations.
The School Teacher Review Body, which advises ministers on pay, said earlier this year that executive heads should be paid up to 20 per cent more. With performance bonuses that would push the top earners towards pound;200,000 a year.
Mick Brookes, general secretary of the National Association of Head Teachers, said it was right that well-paid heads had their salaries published. But he added: "The average wage for a primary head is around pound;50,000, which is a decent salary. But if you look at the hours they are working it is only about pound;20 an hour. Someone earning three times that is getting pound;60 an hour, which is still much less than many other professionals earn."