The "Co-bikes" are currently available from five sites in Exeter, including the central train station, the university and Sowton Park and Ride.
It's hoped that by spring 2017 there will be eight hubs around the city.
The initiative has been launched with support from Department of Transport, while Devon County Council has helped to fund the scheme.
Mark Hodgson, Managing Director of Co-bikes, said: "After years of planning, we're very excited to be launching Co-bikes in Exeter.
"The Co-bikes electric bikes are changing the way that people travel around the city and are affordable and easy as well as being great fun to ride", he added.
For people who choose to become members, the service will cost 75p for 30 minutes, while non-members will pay double.
The bikes have small electric motors which can travel distances of between 40 and 60 miles, and allow speeds of up to 15mph.
The UK's first city-wide electric bike scheme has been launched in Exeter.