Britain is to be hit by its first “pollution charge” with owners of large cars taxed £25 a day to drive into city centres.

Up to a fifth of vehicles, including people carriers, 4x4s and luxury saloons, will be targeted by an emissions-based charge designed to penalise the highest-polluting vehicles.

Smaller cars, such as diesel hatchbacks and hybrid vehicles that emit 120 grams or less of carbon dioxide per kilometre, will be exempt. Those emitting up to 225g/km would be charged £8.

Details of the new charge will be outlined this week by Ken Livingstone, the London mayor. It is set to be introduced in February.

The charge will be watched closely by at least 10 other cities considering their own levies, including Cardiff, Birmingham, Manchester and Cambridge.

Under current plans, drivers going into Manchester are likely to pay at least £5 a day from 2012. Three borough councils in London have already introduced higher parking charges for fuel-inefficient vehicles.

The London congestion charge was introduced in 2003 to cut traffic but it has become less effective. Traffic fell 30% in the first year but is now only 8% below precharging levels. The levy is gradually being transformed into an environmental tax. Vehicle excise duty, the annual tax paid nationally by all drivers, has already been modified so high-polluting cars pay more.

The main losers under the new proposals will include thousands of drivers of larger vehicles living inside the congestion charge zone who are entitled to a 90% discount. In future, they would pay the same rate wherever they lived. This would mean someone living inside the zone and using a large car every day could pay £6,500 a year.

A Transport for London spokesman said that “by making these changes to the congestion charging scheme we are encouraging people to take into account the impact of their choice of car on climate change.”

Edmund King, executive director of the RAC Foundation, said: “The objective was meant to be reducing congestion, but now the goalposts are being changed and you have to question whether motorists are getting value for money.”

Citroën, which has 23 models each generating less than 120g/km, would benefit the most. A spokesman said: “Customers will no longer have to buy an electric car or even a small car to avoid charges. Low emission engines mean family-sized models like the C4 are exempt.”