Two pentasaccharides suitable for conjugation, namely 3-aminopropyl glactosylgloboside and its beta-D-GalNAc-(1-->4)-alpha-D-Gal-linked positional isomer, were synthesized from 3III,4III-di-O-unprotected globotrioside and the trichloroacetimidate of beta-D-Gal-(1-->3)-beta-D-GalNPhth derivative. Glycosylation at both positions led to the formation of beta-D-GalNPhth-(1-->4)-alpha-D-Gal and beta-D-GalNPhth-(1-->3)-alpha-D-Gal-linked products in a ratio of 1:1 without selectivity. Complete NMR spectral assignments are also described.