Local authorities which want to start charging people to drive in their areas are being urged to bid for part of an £18m fund.
Mr Darling says the UK has a duty to address congestion problems
Transport Secretary Alistair Darling said the cash was being made available over the next three years to support "local demand management schemes".
He said £2.5bn would be available under the Transport Innovation Fund by 2014-15 to back road pricing schemes.
But he scrapped plans to bring in road user charging for lorries in 2008.
In a Commons statement, Mr Darling said he hoped the innovation fund cash would offer an incentive to local authorities to come up with ways of dealing with congestion.
He said he believed the UK had "an obligation to look at the problems we face over the next 20-30 years and to do something about them".
Without "radical measures" road congestion would get worse, he said.
"Road pricing is about making journey times by car more reliable for motorists by getting more out of the road network," he said.
The Transport Innovation Fund would offer "substantial long-term investment" and would support "smarter and better management of road capacity we have", he said.
Up to £200m a year would be ultimately available to support local pilot schemes.
"We want to work with local authorities to develop and implement a pilot scheme for road pricing," said Mr Darling.
"No decisions have been taken on where a pilot might take place. We hope to identify partner authorities willing to work up pilot proposals within the next year."
Mr Darling also announced that plans to introduce distance based lorry charging in 2008 would now become part of his proposed wider national road pricing policy.
That decision provoked anger from the Freight Transport Association which had hoped foreign lorries would be charged for operating in the UK in the same way UK vehicles are charged for operating in Europe.
Tory shadow transport secretary Alan Duncan accused Mr Darling of introducing congestion charging by the "back door".
"This innovation fund is not in any way about helping local authorities devise integrated transport policies for their local area," he said.
"It is the Trojan horse through which nationwide congestion charging will be established throughout the UK. Why couldn't you have been honest and straightforward about that?
"This is not about innovation. It is about centralisation and the imposition of road pricing.
"The supposed benefit to local communities is in fact an extension of the central power of ministers to direct money where they choose outside the usual system of allocating funds and to establish road pricing through the back door."
Mr Darling rejected the accusations, adding that there had been a "surprising amount of interest" from different parts of the country in the scheme.
Tom Brake, for Liberal Democrats, said his party agreed that radical measures were needed to deal with congestion and that it was sensible to implement pilots first.