The charges, aimed at cutting congestion, would replace road tax and petrol duty.
Alistair Darling, Transport Secretary, said change was needed if the UK was to avoid the possibility of "LA-style gridlock" within 20 years.
Every vehicle would have a black box installed to allow a satellite system to track its journey, with prices starting from 2p per mile in rural areas.
Darling says: “The advantage is that you would free up capacity on the roads, you would reduce the congestion that we would otherwise face and you would avoid the gridlock that you see in many American cities today.
"This is a prize well worth going for. We've got to ask ourselves, would it work?
“Could it bring the benefits that I believe it could bring, because it would make a real change to the way we drive in this country."
The Department for Transport says the scheme would be fairer because those who travel greater distances would pay the most.
Concerns the tracking system would lead to the state knowing where people were all the time, would have to be addressed, said Darling.
But he told BBC Radio 4's Today programme: "It will mean taking some stick. There are a lot of difficult decisions to be taken.
"I honestly think road pricing could provide us with a way of managing our roads, of getting more out of it, which must be good for us as individuals as well as the country as a whole."
If public reaction is favourable, a pilot scheme planned for the Leeds area could be rolled out nationwide within the next 10 years.
The Environment Agency's Nick Rijke warned that shifting money away from fuel duty would take away the incentive for people to use green vehicles.
AA Motoring Trust director Bert Morris, said: "Tourism is car-based in this country. Would we have empty hotels on summer days on the coast if people couldn't afford to drive?"
It was also important to ensure that drivers with less money were not penalised, Morris added. Mike Rutherford, from the pressure group Motorists' Association, said he feared the Government's main motive for introducing the scheme was "profiteering".
RAC Foundation spokeswoman Sue Nicholson said the plan could help counter a projected 45% growth in congestion problems by 2030.
"Providing this tax was substitutional to fuel tax and road tax and provided we had some other guarantees then I think, for a lot of people, this would be a tempting option," she said.
Environmental group Friends of the Earth broadly welcomed road charging but warned the transport crisis could only be tackled if money raised was invested in improving alternatives to car travel.
Professor Garel Rhys, director of the Centre for Automotive Industry Research at Cardiff university's business school, said: "The key is trying to introduce those tolls without affecting the flow of traffic, i.e. not having to stop and pay at a booth which caused congestion itself.
"Governments will upset at their peril society's wish to do what it wants to do and that is to move around."