Liquid crystalline (LC) black copolymers comprising polystyrene and Le polyester blocks were obtained by a three-step procedure. In a first step, hydroxyl-terminated oligoesters were obtained by polycondensation reaction of methylhydroquinone and 4,4’-dicarboxy-1,10-dibenzoyloxydecane in pyridine solution in the presence of tosyl chloride and dimethylformamide. Hydroxyl-terminated oligoesters were then further polymerized with 4,4’-azo-bis(4-cyanopentanoyl chloride) to form azo-macroinitiators which, in a third step, were employed in the free-radical polymerization of styrene to form block copolymers. The thermal and LC properties of the copolymers are presented and discussed in terms of the dependence upon the molecular weight of the polystyrene block.