The highest polluting vehicles will pay a daily charge of £25 to enter the congestion charge zone, London Mayor Ken Livingstone has announced.
The majority of cars are unlikely to be affected by the price increase
He also revealed that cars with the lowest carbon dioxide (CO2) emissions will get a 100% discount on the charge.
Most drivers will still pay the £8 road toll for entering the zone which covers parts of central and west London.
The new charges come into force on 27 October. The mayor said: "There will be losers but overall we will all gain."
Transport for London (TfL) estimates about 33,000 vehicles that will now fall into the £25 charge sector drive into London each day.
It predicts about two-thirds of these will no longer come into the charge zone once the new fee is introduced.
The £25 charge will apply to vehicles emitting more than 225 grams of CO2/km (g/km), as well as those registered before March 2001 which have engines larger than 3,000cc
Those vehicles getting a 100% discount will emit less than 120g/km.
Of cars currently being driven in the congestion charging zone, 17% would be liable for the £25 charge and just 2% for the total discount
London's transport commissioner, Peter Hendy, said the new charges were likely to bring in £30m to £50m a year.
"Nobody needs to damage the environment by driving a gas-guzzling Chelsea tractor in central London," Mr Livingstone said.
"The CO2 emissions from the most high-powered 4x4s and sports cars can be up to four times as great as the least polluting cars."
He said TfL would closely monitor the scheme, adding that it was flexible and that charges and exemptions could be varied in the future.
"If everybody in London stayed with the same car they've got, but with a less polluting engine, we would reduce carbon emissions in London by 7%," the mayor added.
"What we get out of this is the money to invest in massive expansion of cycling and walking initiatives, so not only do we reduce carbon emissions but we are healthier."
But reaction to the scheme has been mixed.
Sheila Rainger, acting director for the RAC Foundation, said: "The congestion charge was originally developed to reduce congestion.
"Changing this will confuse the public and reduce support and trust for future initiatives."
A spokesman for business group London First said it was "just daft" and would "encourage gridlock".
And the National Alliance Against Tolls said: "This move is not based on logic but on the whipping up of prejudices against those who use these particular vehicles."
Mr Livingstone's political rivals also spoke out against the changes.
Brian Paddick, the Liberal Democrat candidate for London Mayor, said: "What Ken Livingstone is proposing is an emissions charge and it will do nothing to tackle congestion."
Boris Johnson, the Conservative candidate for London Mayor, said: "In effect, the mayor has just given the green light for richer people to buy smaller cars and enter the zone for free while families who struggle with one big car are left feeling the pinch."
But it was welcomed by environmental groups Greenpeace and Friends of the Earth who said it would encourage people to choose greener cars.
The congestion charge was initially introduced in February 2003 and covered just central London, with the daily charge set at £5.
Since then the charge has gone up to £8 a day and a western extension, incorporating such areas as Kensington and Chelsea, has been added.