Abstract Several amphiphilic block copolymers based on vinyl ether derivatives were synthesized by living cationic polymerization. Different compositions of hydrophilic and hydrophobic segments in the copolymers were achieved by changing the monomer ratios of vinyl ether derivatives. Partially deuterated copolymers at ether substituent parts were especially prepared for SANS experiments. These copolymers formed micelles of core-shell structure in water. SANS measurements for aqueous solutions of various copolymers were performed by using a contrast-variation method. The morphology of these micelles was studied as a function of chemical composition of the copolymers.