Revenue Quebec has already seized assets worth $210,000 from a 34-year-old Nuns' Island resident.
Sgt. Daniel Thibaudeau said the alleged scheme involved fictitious companies which were used to evade taxes.
According to police, more than $14.5 million was illegally withdrawn from frozen retirement funds, which deprived the government of tax revenue.
More than 100 officers and investigators executed 14 search warrants on business offices, private homes and postal offices Wednesday morning in the Montreal region.
According to provincial police, more than 300 clients profited from the criminal organization across four continents.
The suspects, who range in age between 28 and 54, are expected to appear in court later Wednesday.