The nitroxide-mediated living free-radical polymerization of 1,2,5,6-di(isopropylidene)-D-glucose-2-propenoate was achieved in dimethylformamide at 105 degreesC with an alpha-hydrido alkoxyamine initiator functionalized with a lipophilic N,N-di(octadecyl)amine group, The kinetics of the polymerization were investigated, and the mechanism was shown to be a living process allowing, after hydrolysis, controlled molecular weight, low-polydispersity lipo-glycopolymers to be prepared. The amphiphilic character of the macromolecule could be altered by either the exchange of the alkoxyamine at the chain end with hydrogen or the preparation of copolymers with lipophilic monomers such as N,N-di(octadecyl)acrylamide. The surface and membrane-forming properties of these novel lipopolymers demonstrate their amphiphilic character.