4-O-α-D-Glucopyranosyl-L-rhamnose has been synthesized in 40% overall yield by condensation of 2-O-benzyl-3,4,6-tri-O-p-nitrobenzoyl-β-D-glucopyranosyl bromide with methyl 2,3-O-isopropylidene-α-L-rhamnopyranoside in nitromethane using mercuric cyanide as acid acceptor. The methyl glycoside hexaacetate was obtained crystalline.