Business Secretary Vince Cable has urged "more discipline" in public sector pay after it was disclosed that 172 civil servants are paid more than the prime minister.
The salaries of those earning over £150,000 were revealed for the first time in a bid to aid transparency.
Office of Fair Trading chief executive John Fingleton, whose annual package is up to £279,999, is the top earner.
Mr Cable said big rises in salaries were not "affordable".
David Cameron, who is paid £142,500 a year, has set out a series of items Whitehall departments must make public in a bid to remove what he called a "cloak of secrecy" around government.
The salary and perks packages were revealed as part of that pledge to give the public more access to official information.
Among other top earners are NHS chief executive David Nicholson, who is paid up to £259,999 and Joe Harley, the IT Director General and Chief Information Officer at the Department for Work and Pensions, who gets £249,999.
Some 28 of those earning over £150,000 are in the Ministry of Defence, but just three are based in the Department for Transport.
Permanent secretaries - who head up government departments - are paid between £150,000 and £200,000 a year.
Cabinet Office Minister Francis Maude said: "By being open and accountable we can start to win back people's trust.
"Openness will not be comfortable for us in government, but it will enable the public to hold our feet to the fire. This way lies better government."
He added that "transparency" was key to the coalition government's efficiency drive and would enable the public to help "deliver better value for money in public spending".
Business Secretary Vince Cable told BBC Radio Scotland he had written to university and college heads to say they should "look afresh" at remuneration, adding that more realism was needed across the public sector.
"There has been massive pay inflation in top salaries, people in the public sector trying to emulate what's been happening in the private sector and it frankly is not affordable," he said.
And former Foreign Secretary David Miliband said more openess about the pay of top officials was "right".
"There needs to be proper accountability," he told BBC Radio 5 Live.
"In some specialist areas there will be the need to pay more. I think the commitment of people in public service, those who commit to public service, is fundamentally not driven by money but they need to be properly rewarded."
Private sector comparison
The union which represents civil servants said it had no objection to the details being published, stressing they represented the pay of about 170 people in an organisation of more than 500,000 staff.
"These are relatively high salaries compared to the average but they are modest in many, most cases compared to the private sector," said Jonathan Baume, general secretary of the First Division Association.
"They are the jobs at the very top of an enormous organisation operating across the United Kingdom."
The BBC's Mike Sergeant said some "ambitious civil servants" might be tempted to use the list of salaries to "push for higher rewards".
"The government hopes the opposite will happen - that revealing these names will create public pressure to keep senior pay down across Whitehall," he added.