Around 700 school leaders are earning six-figure salaries, official figures show.
Data published by the Department for Education reveals that 200 heads working in publicly funded schools are earning upwards of £110,000.
A further 500 had salaries of between £100,000 and £109,999.
It means they are earning double that of the average school leader in a state school, which currently stands at £55,500.
The statistics, which give a snapshot from November 2011, reveal differences in pay between school leaders and teachers, and between academies and local authority-run (maintained) schools.
It shows that 300 academy leaders were earning in excess of £100,000, compared with 400 heads working in other state schools.
But the average salary for a school leader in an academy is higher, standing at £61,500.
The average for heads in schools under council control is £54,600.
At the other end of the scale, 1,600 school leaders were taking home salaries of less than £40,000 in November last year. Of these, the majority were working in maintained nursery and primary schools.
Primary leaders are likely to be paid less as their schools are smaller.
Many academies teach secondary-age pupils which may account, in part, for higher salaries in these schools.
The figures also show that average pay for heads working in maintained schools has risen slightly, to £51,800 from £51,500 in primaries and to £60,900 from £60,700 in secondaries.
But pay for classroom teachers in these schools has fallen to £34,400, from £34,700 the previous year.
The DfE's data also shows that 5,600 class teachers are earning £50,000 or more.
And 34,500 are paid less than £25,000. Of these, 28,000 were working in maintained schools.
A DfE spokesman said: "We have given academies freedoms on pay and conditions because we want them to be able to attract and retain the best staff, and to allow them to be innovative in creating extra incentives if they wish.
"We are seeing that the majority of schools that have become academies do not make changes to pay and conditions immediately. Where they do want to implement changes, it is because it is in their interests to attract the best staff and so terms and conditions in academies are likely to be at least as attractive as those offered in maintained schools."
Christine Blower, general secretary of the National Union of Teachers, said: "For the first time in generations, classroom teachers' average pay actually fell between 2010 and 2011.
"A two-year pay freeze, long-term cuts to teacher pensions and an increase in pension contributions has led to this parlous state.
"One-third more teachers are choosing to retire early on reduced pensions than four years ago.
"Add to that an unacceptable workload, continual inspection and criticism from government at every turn, recruitment into the teaching profession will become increasingly difficult."
Brian Lightman, general secretary of the Association of School and College Leaders, said: "The figures on average pay cover a huge variety of schools. Leading a 60-pupil primary school with 10 staff is a much different job than running a 2,000-pupil secondary school with 200 staff and a budget of £8 million.
"This is reflected in senior leaders' pay and in this context, it's not surprising there is a wide range between the top and bottom of the scale.
"For heads running the biggest and most complex schools, and in more and more cases overseeing more than one school, it is right that their pay reflects the level of responsibility and accountability they have taken on."
Wednesday's statistics also show that the numbers of teachers in England's state schools has fallen to 438,000 from 448,100 in November 2010.
Lightman said: "It's not surprising to see that the number of teachers has decreased. We predicted two years ago that as budgets were cut, some schools would have to make hard decisions about staffing levels as the only way to make ends meet.
"Often this is done by not replacing retiring teachers like for like but increasing class sizes slightly, shifting responsibilities among staff and using teaching assistants and support staff more effectively."
The DfE said the drop was largely down to a drop in the number of "centrally employed teachers".
These are teachers employed by councils to work in areas such as home tutoring or hospitals.
A DfE spokesman said: "The main reason for the drop in teacher numbers is because local authorities do not need to directly employ as many teachers because more schools are becoming academies."
He added: "Schools though are free to organise themselves as they see fit. They are best placed to make these decisions without undue or unnecessary influence from government."