A novel liquid crystalline polymer bearing azobenzene groups in both main chain and side chain has been successfully synthesized by atom transfer radical polymerization (ATRP). Dual bromide-terminated azobenzene was used as the initiator for the ATRP of azobenzene-containing monomer (M6C). The structure of the resulting polymer was confirmed by nuclear magnetic resonance (NMR), and the molecular weight and its dispersity was characterized by gel permeation chromatography (GPC). The mesomorphic properties of this novel polymer were characterized by means of polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The results demonstrated that this polymer can form mesophases.