Details compiled by campaign group the TaxPayers' Alliance (TPA) showed the number earning in six figures fell 11% in 2011-12.
But 103 councils were employing more staff on that level than before - and one executive was handed almost £600,000.
The latest edition of the town hall "Rich List" - assembled using data from annual accounts - found 2,525 council employees pocketed £100,000 plus, compared with 2,839 in 2010-11.
Some 636 staff received over £150,000, and 42 over £250,000. According to the report, the highest paid across the UK was Katherine Kerswell, former group managing director of Kent County Council. Her total remuneration was said to be £589,165 - although that included a sizeable redundancy package.
Matthew Sinclair, chief executive of the TPA, said: "It is good news that the number of senior council staff making more than £100,000 a year is finally falling, although that may only be because many authorities have finished paying eye-watering redundancy bills. Sadly, too many local authorities are still increasing the number of highly-paid staff on their payroll, some of whom are given hundreds of thousands of pounds in compensation just to move from one public sector job to another."
"Local government is showing wage restraint as the 11% fall in the number of staff on more than £100,000 a year shows. There has been no national increase in senior pay for five years, including in 2013/14. Incoming chief executives are also receiving salaries that are on average 8% smaller than their predecessors.
"Local authorities work hard to ensure salaries are set at appropriate levels and have created the E-Paycheck system to allow remuneration committees to compare their pay rates with similar councils in other parts of the country."
Meanwhile, public sector union Unison published research showing that 28,000 people in local government earn just £6.30 an hour - 1p less than the new rate for the national minimum wage due to come into effect from October.