The proposal was unanimously endorsed by UNESCO's executive committee in Paris on Thursday after it was backed by the Slovenian government last month, the Ministry of Education, Science and Sport said in a release.
The centre would advise governments, organisations, legal entities and the general public on systemic and strategic solutions in implementing AI.
It would also set up similar research centres around the world, develop training programmes and create a network to exchange research and know-how.
Its aim is to provide an open environment fostering research and discussions and providing public and political support for AI guidelines and action plans around the globe.
The centre would be at first hosted at the Jožef Stefan Institute (IJS), one of the Slovenian AI pioneers and the country's leading research centre.
The IJS launched AI research in 1972 and set up its AI lab a few years later. Over 180 of its 950 researchers are estimated to be able to take part in various research activities of the new UNESCO centre.
The other Slovenian pioneer in AI is the Ljubljana Faculty of Electrical Engineering, which established the first AI lab in 1981.
Ministry data shows there are some 30 AI research organisations in Slovenia at the moment.
The final green-light for the new AI centre needs to come from the UNESCO conference, which is expected in November.