Communication: A new series of AB liquid crystalline (lc) block copolymers was synthesized via living anionic copolymerization of styrene as segment A and 6-[4-(4-cyanophenylazo)phenoxy]hexyl methacrylate (1) as segment B. The copolymers were successfully prepared in quantitative yields and with narrow molar mass distributions. The number-average molar mass of the segments was varied well-defined The polystyrene block ranged from 3 500 to 7 400 g/mol. The content of the B segment ranged from 1 to 54 wt.-%. Thermotropic phases were detected by differential scanning calorimetry (DSC) for block copolymers with an lc segment of more than 30 wt.-%.