In the most significant challenge yet to the centre-left Italian government's policy of distributing across the country the thousands of migrants arriving at southern ports, Virginia Raggi said it was "time to listen to the citizens of Rome."
"We cannot permit the creation of more social tensions," Raggi, a member of the populist Five Star Movement, wrote on her Facebook page.
"That is why I am saying it is impossible, risky even, to think about creating any new reception structures."
With existing facilities jammed full, Italy is dealing with a mounting backlog of recently-arrived migrants as a result of neighbouring states tightening their borders, making it harder for new arrivals to reach preferred destinations in northern Europe.
As of yesterday, Italy had registered 61,903 new migrants in 2017, up from 52,275 in the same period of 2016. Arrivals generally peak over the summer months when sea conditions make it easier for traffickers to launch boats from Libya.
Processing records suggest at least 40 per cent of them have a valid claim to asylum in Europe or leave to remain on humanitarian grounds.
The others, classified as illegal economic migrants, are liable to be deported but that is often difficult to organise because their countries of origin frequently refuse to take them back.
It is not the first time Italy's government has been confronted by a local authority threatening not to take its share of migrants.
Raggi's move came on the same day that Five Star's leader, Beppe Grillo, announced a crackdown on ethnic Roma migrants from eastern Europe living in makeshift camps in the Rome area.
"Now the music in Rome changes," Grillo wrote on his blog. "Anyone who declares themselves penniless and drives a luxury car will be out. Anyone who begs in the metro with kids in tow, is out. Surveillance against pickpockets in the metro will be increased."
The pressure on Italy's refugee system has been exacerbated by its EU partners reneging on promises to take in asylum seekers under a scheme aimed at relocating 160,000 people from Italy and Greece to other EU states.
As of June 5, only 5,694 people had been relocated from Italy and several eastern European countries are refusing point blank to comply with the scheme.
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