6-O-Unprotected glucose 1, 2-O-unprotected glucose 3, 2,3,4-O-unprotected glucose 6, and 2,3,2′,3′ ,4′-O-unprotected lactose 10 furnished in presence of sodium hydride as base and decyl trifluoromethanesulfonate as alkylating agent exclusively anomeric O-alkylation products 2, 4, 7, and 11, respectively, when dichloromethane or toluene were used as solvents. In tetrahydrofuran as solvent, in addition, participation of the solvent in the anomeric O-alkylation process was observed. Thus, it was found that O-protection is only required to facilitate solubility of the starting materials but not for regio- and stereoselective anomeric O-alkylation.