Vinyl ether (VE)-based amphiphilic block copolymers with D-glucose residues as hydrophilic pendants were synthesized by CH3CH(OiBu)Cl/ZnI2-initiated sequential living cationic copolymerization of 3-O-(vinyloxy)ethyl-1, 2:5, 6-di-O-isopropylidene-D-glucofuranose (IGVE) and isobutyl VE (IBVE) and subsequent deprotection. The precursor block copolymers had a narrow molecular weight distribution (M-w/M(n)similar to 1.1) and a controlled segmental composition. The solubility characteristics of the amphiphilic copolymer depended strongly on composition. Their solvent-cast thin films were examined, under a transmission electron microscope, and could be seen to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition. The amphiphilic copolymers with the appropriate segmental composition were found to form a stable monolayer at the air-water interface, which was successfully transferred onto a substrate by the Langmuir-Blodgett (LB) technique. The layered structure of the built-up LB films was controlled by blending the homopolymer.