Norbornene derivative with a functional group of pendent azobenzene was synthesized and the addition copolymerization and homopolymerization of the product were carried out using the catalytic system of bis-（β-keto-naphthylamino）nickel（II）/B（C6F5）3 in toluene.Then,the polar monomer and the polymers were characterized by means of IR,1H NMR,13C NMR,UV,GPC,TGA and DSC.The results show that the polar monomer and the polymers all exhibit broad optical absorption in the range from 300 to 400nm,that the relative molecular mass of the copolymer and the homopolymer are respectively 4.78×104 ～5.15×104 and 6.5×105～1.28×106,that the introduction of alkyl chain decreases the glass transition temperature of the polymers to less than 573K,that the polymers are of strong thermal stability and the thermal decomposition temperature is up to 593K,and that the solubility of the copolymer is better than that of the homopolymer.