The car will be made available on a lease arrangement to selected UK corporate customers.
It has a top speed of 60mph and a range of up to 70 miles, the smart is exempt from vehicle excise duty and the London congestion charge.
Coventry City Council will be using the car in its fleet of pool vehicles.
Cllr Gary Ridley said: "To make its running costs even greener, the electricity used to recharge the car is from renewable resources.
"As the biggest employer in the city, we should be leading by example and encouraging other businesses to think about their carbon footprint and their impact on their environment while carrying out their day to day activities."
The market trial is being supported by Cenex, the UK’s first national centre of excellence for low carbon and fuel cell technologies.
More information can be found at www.cenex.co.uk.