Most of the suspects, who were picked up in 25 municipalities, have already appeared in court on several charges, including possession, distribution and production of child pornography.
Lt. Jean Lafreniere told a news conference in Montreal on Thursday that some suspects may be charged with sexual assault.
The operation began this summer and included the RCMP and other municipal police forces.
"Since the beginning of the inquiry, one of the individuals distributed most of this material on the Internet all over the world," Lafreniere told reporters.
The provincial police official, who investigates the exploitation of children online, also said repeat offenders were among those arrested.
"One individual had already been arrested by investigators several years ago, while he was involved in luring," Lafreniere told reporters.
Police allege a five-year-old boy was the victim of one of the accused.
The Portage de Prevost centre north of Montreal, which helps drug addicts kick their habit, announced that its director was among those arrested.
Francois Bourdon is accused of accessing, possessing and distributing child pornography from his home computer, according to the centre. It also said he was immediately removed from his functions.
In all, authorities seized 28 computers and filed 61 charges against the various accused, with other arrests in the works.
They also say they have laid their hands on several hundreds of thousands of files — most of them from outside the country.
But so far, there are no indications the accused were part of an organized network.
"An analysis of the computer systems could eventually turn up certain links between these people," Lafreniere added.
Justice Minister Peter MacKay, who was at a security conference in Halifax, said the arrests demonstrate that laws are "having the desired effect."
"We've made it a priority as a government to toughen the legislation with respect to child pornography, sexual assaults, and that's why we've introduced in many cases mandatory minimum penalties," MacKay said.
"That's sending a clear signal that certain crimes are so heinous and of such a nature that they require imprisonment and they require segregation from society. That is the message that we will continue to send and we are looking at other provisions of the Criminal Code for introduction for legislation this fall."