Under a scheme called Zity, the carmaker has joined with urban transport services operator Ferrovial to provide the cars across the country's capital, accessible to customers via a smartphone app.
Madrid already restricts the use of cars with traditional internal combustion engines during times of intense air pollution, and plans to permanently ban ICE engines from its centre in the middle of next year.
Parking is free for electric vehicles in the city.
With a driving range of up to 285m in real world conditions, the supermini Zoe is Europe's best selling electric car.
