Aryl 1-thioglycosides have directly been synthesized in good yields from the corresponding unprotected sugars and thiols without protection of the hydroxy groups by using 2-chloro-1,3-dimethylimidazolinium chloride (DMC) as dehydrative condensing agent. The reaction proceeded in a mixed solvent of water and acetonitrile under mild reaction conditions, leading to the predominant formation of beta-anomers.