Speaker of the House of Lords Baroness D'Souza ran up a £230 bill as she kept a chauffeur-driven Mercedes waiting for four hours while she watched opera only a mile from Parliament.
Other details of high spending were revealed from a Freedom of Information request which showed how she kept a car waiting for four and a half hours while she dined with the Japanese ambassador, at a cost to the taxpayer of £270.
She also spent tens of thousands of pounds on travel, flew business class and stayed in hotels costing up to £300 pounds a night, according to the Press Association.
She is also understood to have spent £738 keeping a Mercedes parked for up to 10 hours during an event at Windsor Castle. In addition, using a Mercedes to travel from Westminster to Canterbury for the enthronement of Archbishop Justin Welby in March 2013 cost £627.
The records showed she spent nearly £26,000 on a ten-day trip with three officials to Japan, Hong Kong and Taiwan.
A House of Lords spokesman said: 'The Lord Speaker usually drives herself to events she attends as a representative of the House of Lords.
"However, at events she has attended at high-profile venues, the security requirements of the hosts often require that she is brought in a car which must also wait for her departure.
"The hosts often do not permit a separate car to be sent to collect guests for security reasons. The Lord Speaker's Office always explores the possibility of booking separate cars in order to ensure best value for money."
However the Taxpayers' Alliance political director Dia Chakravarty said that many would be "dismayed" by the revelations.
"Whoever has been making her travel arrangements urgently needs to reassess whether they have been achieving value for money and amend future plans accordingly.
'People will struggle to conclude that her present spending on travel is anything other than wasteful and occasionally downright frivolous," she said.
It emerged five months after the Commons Speaker, John Bercow, faced heavy criticism for running up similar bills travelling to functions around London.