Road pricing trials will begin in 2010, and they could lead to drivers paying up to 1.30 a mile to use key roads at busy times.
The trials will be run in Leeds, North Yorkshire, Buckinghamshire, south-west London, Essex, Suffolk and Milton Keynes.
In each area 100 motorists will carry black-box satellite-tracking systems that monitor where, and when, a car has travelled.
The testing programme will start in January 2010, with additional members of the public to be invited to volunteer to join the trials later in the year.
The Government hopes that it can ease congestion by charging for using the busiest roads and keeping it free to travel on quieter roads.