More than 1,000 heads are earning in excess of £100,000 a year, according to research from the TaxPayers' Alliance.
It highlights the pay of the heads of two east London secondaries - one who its says earned £279,000 in 2013/14 and another £220,000.
In all, amid pay freezes across the public sector and several teaching staff strikes in 2013/14, there were 110 school leaders who received annual remuneration greater than £150,000.
The research, compiled from Freedom of Information requests and analysis of annual statements of accounts, took into account employees' salaries along with expenses and allowances.
Jonathan Isaby, chief executive of the TaxPayers' Alliance, said: "Taxpayers will not begrudge an inspiring headteacher or world-class academic a good salary if they produce great results and motivate their students, but too often this is not what we find.
"The pay and perks enjoyed by those working at our schools and universities - and indeed across the entire public sector - must more accurately reflect how well they are doing their jobs."
Christine Blower, general secretary of the National Union of Teachers said: “Until relatively recently there was a coherence to the salaries received by teachers and head teachers. With the almost complete deregulation of the pay structure and the introduction of performance related pay it would seem that some senior members of the teaching profession are paying themselves salaries that are massively more than those of classroom teachers.
“It should come as no surprise that the gap between the salaries of those in leadership positions and classroom teachers is wider in academies than in other schools, since pay de-regulation has been at the heart of the academy programme from the start.
“Teachers will be dismayed at this growing inequality while they continue to face a depression in pay. We need to have one system for teachers’ and head teachers’ pay that applies across the board with transparent and fair arrangements for pay progression.”