Eduard-Stefan Georgescu was nabbed on Friday as he left Bordeaux jail.
He faces 32 new charges, including armed sexual assault, sexual assault, attempted kidnapping, and weapons possession.
Capt. Nancy Colagiacomo, a Longueuil police spokeswoman, said the break in the case came after a Montreal woman who had been assaulted came forward last November.
"She kind of tipped us off that she probably recognized him as being the same suspect," Colagiacomo told a news conference Monday afternoon.
"That was what gave the break to the Longueuil police in order to verify this information. It all came after that, it all corresponded."
She said there was also some DNA evidence involved and that Quebec provincial police had helped create a profile of the suspect.
The alleged assaults on Montreal's south shore occurred between 2007 and 2012.
Eleven alleged victims have come forward but police say they are investigating the possibility there are more.
The alleged victims are between 13 and 29.
Police say Georgescu would approach women and ask them for directions before allegedly assaulting them.