Reaction of equivalent amounts of pentaacetyl-β-D-glucopyranose and methanol in benzene or chloroform solution in the presence of 0.5 or more moles of stannic chloride per mole of methanol gave 50-60% yields of methyl tetraacetyl-β-D-glucopyranoside. α-Acetochloroglucose was a by-product of the reaction. The mechanism of the reaction is discussed. The method was applicable for the preparation of phenyl tetraacetyl-β-D-glucopyranoside.