A novel synthetic pathway toward stereoblock copolymers by combining catalytic chain transfer polymerization with anionic polymerization is described. Catalytic chain transfer polymerization (CCTP) has been used to synthesize vinyl-terminated polymers, which, after the Michael addition of alpha-lithioisopropyl isobutyrate, were used as macroinitiators for the anionic polymerization of methacrylate-type monomers. The resultant polymer consists of a predominantly atactic block (originating from the free radical polymerization) and a more isotactoid or syndiotactoid block (originating from the anionic polymerization).