An efficient method for synthesis of the (1 -> 3)-linked disaccharides is reported. Glycosylations of 4,6-O-benzylidene glucopyranosides with glycosyl trichloroacetimidates regioselectively afforded (1 -> 3)-linked disaccharides in good yields using trimethylsilyl triflate (TMSOTf)/4 angstrom MS as catalyst.