Amphiphilic block and statistical copolymers of vinyl ethers (VEs) with pendant glucose residues were synthesized by the living cationic polymerization of isobutyl VE (IBVE) and a VE carrying 1,2:5,6-di-O-isopropylidene-D-glucose (IpGlcVE), followed by deprotection. The block copolymer was prepared by a two-stage sequential block copolymerization, whereas the statistical copolymer was obtained by the copolymerization of a mixture of the two monomers. The monomer reactivity ratios estimated with the statistical copolymerization were r(1) (IBVE) = 1.65 and r(2) (IpGlcVE) = 1.15. The obtained statistical copolymers were nearly uniform with the comonomer composition along the main chain. Both the block and statistical copolymers had narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight similar to 1.1). Gel permeation chromatography, static light scattering, and spin-lattice relaxation time measurements in a selective solvent revealed that the block copolymer formed multimolecular micelles, possibly with a hydrophobic poly(IBVE) core and a glucose-carrying poly(VE) shell, whereas the statistical copolymer with nearly the same molecular weight and segment composition was molecularly dispersed in solution. The surface properties of the solvent-cast films of the block and statistical copolymer were also investigated with the contact-angle measurement. (C) 2001 John Wiley & Sons, Inc.