Montreal police say around 10:20 a.m. ET on Thursday, the man entered the SAQ Signature store on Sainte-Catherine Street near University Avenue.
After threatening employees with what police believe may have been a handgun, he punched through a locked glass case where the store keeps rare bottles of liquor.
Among the several bottles stolen was a 50-year-old Balvenie single malt scotch priced at $49,500.
The scotch was bought by the SAQ in May 2013 and was one of the last on the Canadian market.
"The person knew what he was doing, as the suspect went to this specific location in the store," said Montreal police spokesman Jean-Pierre Brabant.
The stolen bottles of alcohol have a total value of about $100,000.
The Société des alcools du Québec says additional security has been posted at the store.