The Arena clan, a family belonging to the powerful 'Ndrangheta crime syndicate, allegedly made a killing by supplying services for the centre at Isola di Capo Rizzuto and syphoning off money from the state destined for the migrants.
"Over 500 agents overnight arrested 68 people... Accused of mafia association, extortion, carrying illegal weapons, fraud, embezzlement to the detriment of the state, (and) theft," police in Catanzaro, a city in Calabria, said in statement.
Police arrested Leonardo Sacco, head of the Catholic Misericordia association which officially runs the centre. The 35-year-old has boasted of links to high-powered political figures.
Local priest Edoardo Scordio was also detained in the sting, according to Italian media reports.
Police say they believe the Arena clan, through Sacco, awarded contracts for services such as the centre's food supplies to associations it set up specifically for the purpose, as well as to other 'Ndrangheta families.
The head of the country's anti-mafia commission, Rosy Bindi, said the sting was "an important result in the fight against the 'Ndrangheta and the infiltration of mafia in the management of migrants".
About 175,000 people are currently living in reception centres, where the state provides food, clothing, Italian lessons, psychological support, health care and a small amount of pocket money.
Italy's finance ministry has estimated the 2017 budget for migrant reception at three billion euros ($3.3 billion), depending on how many people are rescued in the Mediterranean and brought to the country.
The Calabrian centre had long been on the authorities' radar: In 2015 Italy's L'Espresso magazine published an investigative report alleging that managers at the camp were stealing funds earmarked for migrants and making money by starving them.
The Crotone prefecture said in 2014 that it appeared the official number of people recorded at the centre was grossly inflated, with management pocketing funds from the state for "ghost" migrants.
L'Espresso said it had got hold of a police report putting the figure at over 10,000 euros a day.
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