The Harris Federation spent at least three-quarters of a million pounds on the wages of its top two earners, its latest accounts reveal.
The academy chain, which runs 50 schools in London and Essex, is now thought to have the highest two earners in the country's state school sector.
The country's highest-paid school leader, Harris' chief executive, Sir Dan Moynihan, saw his salary increase to between £455,000 and £460,000 in 2019-2020 – a salary band rise of £5,000 on the year before.
His employer's pension contribution rose from £50,000 to £55,000 to £70,000 to £75,000.
Harris also paid another member of staff between £300,000 and £310,000.
Academy trust had 41 staff on salaries of £100,000 or more
This is higher than any other salary in multi-academy trust accounts seen by Tes for 2019-20.
These two were among seven people in the English state schools sector paid £250,000 or more in the most recent year.
The highest salary outside of Harris seen in the 2019-20 accounts was at Thomas Telford School in Telford, Shropshire.
Accounts show that a member of staff there was paid between £290,001 and £300,000 in 2019-20, according to the latest accounts filed by Telford City Technology College Trust, which runs the school.
Harris' accounts do not name the person earning just over £300,000.
The number of Harris employees earning six-figure salaries also increased in 2019-20.
Figures show the trust had 329 staff classed as high earners – on salaries of £60,000 or more.
This included 41 staff on salaries of £100,000 or more – up from 31 a year earlier.
It also included 11 staff on salaries of £150,000 or more and four staff on £200,000 or more.
Tables of Harris' highest earners
A Harris Federation spokesperson said: "Harris academies consistently deliver high standards, creating brilliant educational outcomes in disadvantaged communities across London.
"The number of salaries over £100,000 reflects not just the size of our federation but also the reality of the competition, particularly in London, for outstanding school leaders."
Harris said that Sir Dan's employer pension contribution increase was down to the national employers' contribution for all staff, "mandated by the government, which has gone from 16.48 per cent to 23.68 per cent".