His wife Rona's job could prove equally tricky - defending the millionaires who sponsor the Government's controversial academies programme. Mrs Kiley is chief executive of the Academy Sponsors Trust, an exclusive club for the millionaires, businesses and charities who provide thepound;2 million private sponsorship needed for each academy.
Its main role is to support the sponsors, representing them to the Government and in the media.
An independent organisation, funded by a group of the earliest sponsors and the HSBC bank, it holds regular forums so the sponsors can pool ideas and problems.
The trust has not been charged with finding new backers for academies, although its millionaire members "do like to get their friends involved", said Mrs Kiley. She described a recent meeting of potential sponsors. "One of the men turned to his wife and said 'So, should we put pound;2 million into a school - or do we get that house in the south of France?'"
Apart from writing a few letters defending academies, the trust has kept a low profile since its launch last summer. But its influence is expected to grow as the Government expands the number of academies to 200 by 2010. As well as lobbying ministers, the trust tries to act as a buffer between sponsors and the Government.
Many of the sponsors are used to complaining to the person at the top when they hit a snag in their business dealings.
The trust hopes its members will call it first when they have frustrations about their academies rather than ringing Downing Street or senior civil servants. Academy sponsors complain that they face too much bureaucracy and that tax rules are stopping them sharing their school's facilities with the wider community.
"The sponsors get very involved in the academies, and in all the details of running a school," said Mrs Kiley. "They are not naive about what they have to do. But sometimes they get impatient with bureaucracy and other things."
Critics question the educational input schools gain from businessmen such as property developers and car dealers.
But Mrs Kiley says that schools do get special benefits. "The idea of somebody who has resources working very hard on behalf of a school trying to make the connections to improve it and to take real responsibility for what happens is very positive," she said.
She has found press coverage of academies frustrating. The most damaging has been the controversy surrounding those sponsored by the Vardy Foundation, which teach creationism. Mrs Kiley stresses that the Christian nature of the Vardy academies is a matter of "ethos, not conversion".
Mrs Kiley's husband Bob was recently given a new four-year contract worthPounds 2.4 million. The couple moved to England in 2000 when Mr Kiley became the capital's transport commissioner, and they live in a pound;2.1m Belgravia townhouse provided by Transport for London. They have property in the United States, including a summer home in the well-heeled resort of Martha's Vineyard.
Mrs Kiley's previous post was as director of education for London First, where she played a central role in bringing Teach First to the capital. In this project, which copies an American scheme, graduates are sent to work in city schools. Mrs Kiley became involved in setting up the trust through her work on this initiative and discussions with the Prime Minister's education adviser, Andrew Adonis .
Mrs Kiley, born the 1940s in Reading, Pennsylvania, briefly tried teaching while studying for an arts degree at an all-women college in Philadelphia, now part of Arcadia university.
Since then she has had a varied career in the worlds of social work, human rights, education, equal opportunities and nature conservation. Although her job with the sponsors' trust is full-time, she remains a trustee of Teach First, continues to help Human Rights First and was a trustee of the World Trade Centre Disaster Fund.
Mrs Kiley says that as an American she is surprised by the levels of cynicism in Britain and the belief that "the Government should do everything".
"My value system was believing that philanthropy was good," she said. "I have learned that isn't always accepted here."