Amphiphilic and heterotactic-rich poly(vinyl alcohol) (PVA) macromonomer, that is, PVA having a phenyl or phenoxyethyl methacrylate unit as the polymerizable end group, was synthesized via the aldol-type group-transfer polymerization (aldol-GTP) technique. Aldol-GTPs of vinyloxytriethylsilane (VOTES) were carried out in dichloromethane with 4-methacryloylbenzaldehyde and 4-(2-methacryloylethoxy)-benzaldehyde as the initiators with various Lewis acids. The polymerizations proceeded smoothly to give silylated PVA macromonomers (number-average molecular weights: 1.3 x 10(3)-1.96 x 10(4)). Poly(VOTES) was easily desilylated to give heterotactic-rich PVA macromonomer in good yield. The critical micelle concentration of the PVA macromonomer was determined by surface-tension measurement. Micellar polymerization of the amphiphilic macromonomer gave comb-shaped (graft) polymer having PVA side chains effectively (conversion: 80-82%), whereas polymerization in dimethyl sulfoxide (homogeneous state) did not.