Around 2500 officers participated in raids centred on the Calabrian city of Vibo Valentia on Thursday.
Police also seized property worth €15 million in the operation.
“This is the biggest sweep since the Palermo maxi-trial (475 suspects tried in 1986-87),” Cantanzaro prosecutor Nicola Gratteri said in a statement.
The suspects were held on suspicion of extortion, murder, money laundering and belonging to a mafia organisation.
The arrests are part of an investigation which began in 2016 and covered at least 11 Italian regions including Lombardy, Sicily, Veneto, Tuscany and Campania.
Some of those held were arrested in Germany, Switzerland and Bulgaria.
Those arrested include Giancarlo Pittelli, a well-known lawyer from Catanzaro and a former member of Silvio Berlusconi’s Forza Italia (FI) party.
Pittelli, who was also a member of a justice commission and a regional coordinator of Berlusconi’s party, is accused of mafia association.
A former regional official, a mayor, a political party official and a police commander were also among those arrested.
Thursday’s operation also revealed some of the ‘Ndrangheta’s secrets.
In a pizzino, a small slip of paper used by the mafia for top-level communications, the police learned of the phrase that prospective mobsters must say before officially becoming ‘Ndrangheta bosses.
The sentence contains a quote from three 17th-century knights who, according to legend, founded the Cosa Nostra in Sicily, the Camorra in Campania and the ‘Ndrangheta in Calabria.
