Tony Blair, who famously avoided Islington schools for his two eldest sons, last week admitted that low standards are driving other inner London parents away from their local comprehensives.
The Prime Minister's comments on the state of the capital's schools came as he announced a package to improve education in Islington, Hackney, Haringey, Lambeth and Southwark - five of London's poorest authorities.
"It is completely absurd that in this huge, vibrant and exciting city we do not have enough excellent schools so that parents can decide they are going to send their children to a state school," he said.
Mr Blair and his wife Cherie opted for the voluntary-aided London Oratory School in Fulham for sons Euan and Nicky in preference to local Islington secondaries.
His admission follows controversy over the decision by Diane Abbott, the left-wing Labour MP, to reject Hackney secondaries and send her son to the private pound;10,000-a-year City of London School.
Last month Oliver Letwin, the shadow chancellor, had to apologise to Lilian Baylis school, his local Lambeth secondary, after saying that he would rather "go out on the street and beg" than send his children there.
Ten new schools, including seven academies, and seven sixth-forms will open in the five boroughs as part of the London Challenge under plans announced by Mr Blair.
Every secondary will also be able to gain specialist status, be rebuilt or refurbished, equipped with new technology and to become an "extended school", offering extra services such as childcare and adult education.
Schools will also be encouraged to federate, broadening the curriculum available to pupils by allowing them to attend lessons in other schools.
Each borough will get its own tailor-made plan, drawn up with the government, to provide targeted help to schools which need it most.
In Southwark the number of city academies - state-funded independent schools backed by private sponsorship - will double to four. Lambeth will open a new school in West Norwood and an academy on Clapham Common with the possibility of up to two more academies one of which would serve Brixton.
Islington will have a new Church of England-sponsored academy specialising in humanities. In Hackney the new Mossbourne academy will open next year, with two more academies replacing Laburnum and Kingsland schools by 2006, while the new Yesodey Hatorah girls school will provide state education for the borough's orthodox Jewish community from 2005.
A new secondary will be built in the centre of Haringey by 2008 to cope with rising pupil numbers.
Louise Fox, headteacher of Archbishop Tenison school, Lambeth said: "The London Challenge is a magnificent opportunity to get London's schools back on the map."
Wendy Parmley, principal of Archbishop Michael Ramsey technology college, Southwark, which will become a city academy under the London Challenge, said: "This is a marvellous opportunity."
Cheryl Day, headteacher of Clapton girls technology college, Hackney, backed many of the ideas. She said: "I want to know when my school and other Hackney schools that have already achieved significant improvements will benefit from the extra resources.
"More than anything we need a long term commitment to better funding that will improve facilities and give stability to our budgets."