Ecotricity said it has powered more than 30 million miles for free since 2011, but from Monday motorists will have to pay £5 for a 20-minute rapid charge at its electricity pumps.
A spokesman for the firm, founded by green energy tycoon Dale Vince, and based in Stroud, Gloucestershire, said this 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 support the growth of the network, which will remain free for Ecotricity domestic energy customers.
Some 38,000 motorists are registered to access Ecotricity'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.
Earlier this year, Ecotricity became the first energy company to have its logo featured on a motorway service station sign to tell drivers of electric vehicles the location of the nearest charging points.
It appeared on a sign at Sedgemoor services on the M5 in January, with plans also confirmed to roll out the system elsewhere in the country.
Signs at Hamilton on the M74 and Norton Canes on the M6 toll road were said to be the next ones to be given the logo.
Figures from the Driver and Vehicle Licensing Agency showed that there was a huge increase in the number of plug-in and hybrid cars on the roads last year.
The data revealed that there were 45,300 electric vehicles in the UK by the end of 2015, up from 20,500 at the end of 2014 and just 134 in 2010.
The rise of electric vehicles is also being fuelled by technological developments, such as new batteries with lower charging times and increased range.