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PROBLEM TO BE SOLVED : To obtain the subject derivative useful as medicines, agrochemicals, cosmetics, reagents or the like by reacting a hemiacetalized acylated saccharide derivative with an alcohol in the presence of a rare earth perfluoroalkylsulfonate and a specific Lewis acid. SOLUTION : When a saccharide derivative in which hydrogen of hydroxyl group at the anomeric position of a saccharide having the anomeric position bonded through a hemiacetal is substituted with either acyl group of acetyl group and methoxyacetyl group (e.g. 2, 3, 4, 6-tetra-O-benzyl-D-glucopyranosyl acetate) is reacted with an alcohol (e.g. 3&beta -cholestanol) in the presence of a rare earth perfluoroalkylsulfonate (e.g. ytterbium trifluoromethanesulfonate), a boron trifluoride ether complex is made to coexit to thereby efficiently afford a glycoside derivative useful as medicines, agrochemicals, cosmetics, reagents or the like under mild conditions with a small amount of formed by-products.