This paper describes the polymerization of 2-methyl-(3,6-di-O-benzyl-1,2-dideoxy-alpha-D-glucopyrano)-[2,1-d]-2-oxa zoline (1) with an acid catalyst. The polymerization proceeds involving stereoregular glycosylation to give polysaccharide 2. The polymer structure, 2-acetamido-3,6-di-O-benzyl-2-deoxy-(1-->4)-beta-D-glucopyranan was determined by means of H-1 NMR,C-13 NMR, and LR spectra as well as elemental analysis. The molecular weight was at most 4900 (degree of polymerization approximate to 13).