The 'Ndrangheta is widely considered to have become Italy's most powerful organised-crime syndicate thanks to its control over much of the cocaine that arrives in Europe.
Its reach has stretched outside its southern Italian base and gone well beyond the country's borders.
Wednesday's operation involving over 500 officers was concentrated in raids in the Calabrian province of Vibo Valentia, although people were also detained in other parts of Italy.
A total of 167 people are under investigation in the probe linked to Wednesday’s operation, including Andrea Niglia, the former president of the province of Vibo Valentia and ex-mayor of the town of Briatico.
Niglia has not been detained.
Only last week European police carried out the biggest ever operation in the EU against the 'Ndrangheta mafia, making some 150 raids and arresting over 200 suspected mafiosi in eight European countries.
Police also seized huge quantities of drugs, cash and weapons, Belgian and German prosecutors said.
ANSA