D-Glucosamine-containing glycopolymers with well-controlled structure were synthesized by living cationic polymerization. To this end, D-glucosamine-containing vinyl ether(VE) of the type [CH2 = CH(OCH(2)CH(2)OR)] was prepared, where R denotes a 3,4,6-tri-0-acetyl-2-deoxy-2-phthalimide-beta-D-glucopyranoside, i.e., the hydroxyl and amino groups in D-glucosamine residues are protected by acetyl and phthaloyl groups, respectively. It was found that (1) the efficient living cationic polymerization of VE monomer is achieved by a combination of ethylaluminum dichloride (EtAlCl(2)) with an adduct of trifluoroacetic acid (TFA) and isobutyl VE (IBVE) [CH3CH( OiBu) OCOCF3] (i.e., TFA/EtAlCl(2) initiating system); and (2) the polymerization in toluene at the elevated temperature (0 degrees C)is most suitable to proceed the homogeneous polymerization over the whole conversion range. The molecular weight distribution of the resulting polymers was very narrow (<(M)over bar (u)>/<(M)over bar (n)>M similar to 1.1). Quantitative deprotection of the resulting precursor polymers was successfully achieved with hydrazine monohydrate to afford the corresponding water-soluble polymers with pendant D-glucosamine residues.