A police sergeant earned nearly £69,000 in overtime last year, taking his pay to more than £110,000, official figures show.
He was among Metropolitan Police officers who earned a total of £109 million for working extra hours in 2010-11.
The un-named sergeant, who was the Met's top overtime earner, was paid £68,922 on top of his basic salary of about £43,000.
One Scotland Yard police constable received £55,186 in addition to his wages of around £31,000, the force revealed in response to a Freedom of Information request.
It is understood that the large overtime payouts went to specialist protection officers who are regularly sent overseas for work.
Other forces also gave their officers substantial sums for putting in additional hours, with the Police Service of Northern Ireland paying one sergeant £57,000 and a constable £43,000, The Sun reported.
A Scotland Yard spokesman said: "Overtime is called upon when it is essential to maintain operational effectiveness and, in the context of capital city policing and national responsibilities, there are times when there is a genuine need to call on officers to work beyond their scheduled hours to police unforeseen events, to provide security or public reassurance.
"The few officers receiving significant payments in respect of overtime are in roles where working time is determined by the operational circumstances.
"The Metropolitan Police Service is committed to the effective control and management of overtime in supporting the delivery of an efficient policing service and, consequently, there has been a reduction in overtime expenditure in recent financial years."