Amphiphilic block copolymers of vinyl ethers (VEs) of the type - [CH2CH(OCH(2)CH(2)OR)](m) - [CH2CH(OiBu)](n)- were synthesized by living cationic polymerization, where R is a D-glucose residue, and m and n are the degrees of polymerization (m = 20-50; n = 11-89). To obtain them, sequential living block copolymerization of isobutyl vinyl ether (IBVE) and the vinyl ether carrying 1,2:5,6-diisopropylidene-D-glucose residue was conducted by using the HCl adduct of IBVE, CH3CH(OiBu)Cl, as initiator in conjunction with zinc iodide. These precursor block copolymers had a narrow molecular weight distribution ((M) over bar(w)/ (M) over bar(n) similar to 1.1) and a controlled composition. Treatment of them with a trifluoroacetic acid/water mixture led to the target amphiphiles. The solubility of the amphiphilic block copolymers in various solvents depended strongly on composition or the min ratio. Their solvent-cast thin films were observed, under a transmission electron microscope, to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition.