New amphiphilic diblock copolymers of controlled dimensions constituted of styrene and hydrophilic glycosidic vinyl ether moieties were prepared and their emulsifying properties examined. The hydrophobic block was obtained by living anionic polymerization of styrene, followed by a quantitative functional termination with chloroacetal derivatives. The polystyrene chain ends were then derivatized, by addition of trimethylsilyl iodide, into α-iodo ether macro-initiators. The latter were used to initiate the “living” cationic polymerization of protected glycosidic vinyl ethers, in the presence of weak Lewis acids (typically ZnCl2). The amphiphilic copolymers were obtained by deprotection, in acidic medium, of the hydroxy functions of the sugar of the moieties. The solubility characteristics of these copolymers are discussed with respect to the dimensions of the copolymers and to the hydrophilic/hydrophobic balance between the two blocks.