The C4 Picasso made the 600-km (372-mile) road trip between the two main Citroen factories in Vigo and the Spanish capital without the help of a driver at the wheel.
The test was carried out after Spain's traffic directorate adopted new regulations earlier this month that sets the framework for driverless cars.
The ‘intelligent' car that combines GPS and camera sensors, radar and laser scanners to navigate the roads looks no different from any other car but is intended to make road travel safer by removing human error.
However, at the moment regulations only allow the car to be driven on motorways and dual carriageways and restrict use in built up urban areas.
The cars could be on the road within five years.
"The PSA Citroen group intends to equip some of their production cars with self-driving systems from 2018,” explained Jose Leon Capitan, the spokesman for Citroen Spain at a press conference.
"As totally autonomous driving becomes possible in our vehicles by 2020, it will allow us to reduce sensibly the number of car accidents," he said.