For the purpose of carrying out a comprehensive investigation into the nature of the conformational epitope of the type III group B Streptococcus polysaccharide, combined chemical and enzymatic methods were applied to the synthesis of three decasaccharide probes, namely beta-D-Glc-(1-->6)[alpha-NeuR-(2-->3)-beta-D-Gal-(1-->4)] -beta-D-GlcNAc-(1-->3)-beta-D-Gal-(1-->4)-beta-D- Glc-(1-->6)[alpha-NeuR-(2-->3)-beta-D-Gal-(1-->4)]-beta-D-GlcNAc-( 1-->3) -beta-D-Gal-OMe (22 NeuR = NeuAc; 23 NeuR = NeuAc with 8% 13C-labeling; 24 NeuR = NeuPr). The precursor core octasaccharide 21 was chemically synthesized from trisaccharide donor 11 and pentasaccharide acceptor 19 by block condensation. Sialylation of 21 with alpha-(2-->3)-sialyltransferase and CMP-NeuAc afforded 22. In the presence of CMP-sialic acid synthetase and alpha-(2-->3)-sialyltransferase, 21 was sialylated with sialic acid derivatives (8% 13C-labeled, or N-propionyl substituted) to give 23 and 24, respectively. Complete assignments of the 1H and 13C NMR spectra of compounds 21, 22 (23), and 24 are also presented.