A series of smectic C* liquid-crystalline (LC) block copolymers were successfully synthesized via the living anionic polymerization of polystyrene with optically active methacrylate monomers containing (S)-2-methylbutyl 4-(4-hydroxyphenylcarbonyloxy)-biphenyl-4'-carboxylate mesogens. These materials are the first reported smectic C* block copolymers. Anionic polymerization in tetrahydrofuran (THF) at -70 degrees C leads to LC block molecular weights of approximately twenty repeating units. The number-average molecular weight of the polystyrene block was varied from 7000 to 20000 to adjust the composition in the block copolymers. Differential scanning calorimetry and optical microscopy indicate that the smectic C* phase is present in the systems over broad temperature ranges.