The synthesis of two new classes of liquid crystalline block copolymers (1-5) by a two-step combination of cationic and free-radical polymerizations is described. An azomacroinitiator was prepared first by cationic polymerization of tetrahydrofuran or promoted cationic polymerization of cyclohexene oxide, which was then used to initiate the free-radical polymerization of an acrylate monomer containing a variously substituted biphenyl mesogenic group. The semicrystalline and liquid crystalline blocks were essentially microphase-separated and gave rise to different thermotropic mesophases.