Since 2011, Stroud-based Ecotricity has installed nearly 300 electric chargers across the country and powered more than 30 million miles for free.
But from Monday, motorists will have to pay Â£5 for a 20-minute rapid charge at its electricity pumps.
A spokesman for the firm said, it would still be "significantly less" than the cost of running a petrol or diesel car.
He added that a payment system was being introduced to "maintain and grow" the network, which will remain free for Ecotricity domestic energy customers.
The Gloucestershire firm, founded by green energy tycoon Dale Vince, said it had seen usage treble in 2015.
Some 38,000 motorists are registered to access the green energy firm's 296 charging points across the UK.
Sales of new alternatively fuelled vehicles rose by 40% in 2015 to more than 72,000, a market share of 2.8%.
The government's Committee on Climate Change warned last year that 9% of new car sales should be electric by 2020 for the UK to meet its legal obligation to cut greenhouse gas emissions by 80% by 2050 compared with 1990 levels.
Drivers of electric vehicles will soon have to pay to use a major network of charging points.