A series of miktoarm star novel azobenzene side-chain liquid crystalline (LC) copolymers were synthesized by combination of atom transfer radical polymerization (ATRP) and chemical modification of the termini of ATRP-derived polymers. These miktoarm star copolymers carrying one polystyrene (PS) arm and two poly [6-(4-methoxy-4'-oxy-azobenzene) hexylmethacrylate] (PMMAZO) arms were characterized by H-1 NMR and GPC. The liquid crystailline behavior of these copolymers was studied by DSC and POM. It was found that the miktoarm star copolymers have the similar LC properties to PMMAZO homopolymer, and their thermal stability of the mesophases is increased, while the phase transition enthalpies are reduced.