The customised white Kangoo was presented to the pontiff by French carmaker Renault.
Benedict XVI has been dubbed "the green pope" for his environmental concerns.
Since he became Pope, the Vatican has installed photovoltaic cells in its main auditorium and joined a project to offset carbon dioxide emissions.
The city state intends that by 2020, 20% of its electricity will be provided by renewable energy.
Renault said the Kangoo Maxi van, which has the Papal coat of arms on its doors, has a 44 kilowatt electric motor and lithium-ion battery and can travel 170km (105 miles) without recharging.
Renault also handed over a second car, which is blue, to be used by the Vatican's police force.
The vehicles were presented to the Pope on Wednesday at Castel Gandolfo, in the Alban Hills south of Rome, by Renault chairman Carlos Ghosn, before being unveiled to the press on Thursday.
The Pope used his new car on Wednesday to travel from the helipad at Castel Gandolfo through the gardens back to his palazzo, the Vatican said.
He was returning after presiding over his weekly audience at the Vatican.
Vatican spokesman Federico Lombardi said the Pontiff's Kangoo would not be a new Popemobile as it lacked the necessary security features.
The current Popemobile is based on the Mercedes-Benz M-Class and has bulletproof windows.
Pope Benedict XVI has been presented with an electric car to use within the grounds of the Vatican and his summer home of Castel Gandolfo.