There has been much interest in polymerization catalyzed by enzymes ("enzymatic polymerization") asa new methodology of polymer syntheses. Recently, enzymatic synthesis of polyaromatics has been developed. Peroxidase-catalyzed polymerization of phenol and its various derivatives proceeded to give polymers with acomplicated structure, which is hard to synthesize by conventional oxidative polymerizations. As a p2diphenol oxidase, laccase could be used to catalyze the oxidative reaction and macromolecule synthesis. The polymerization of 4-phenylphenol was carried out in the mixture of buffer (pH4) and organic (15：85, vol%) catalyzed by a laccase, produced from white rot fungus, at 35℃for 48h to form a polymer, 2, 62poly (42phenylphenol) with molecular weight above 80,000,which was determined by GPC. The polymer was analyzed by DSC to show that the glass transition temperature is 168184 ℃and the decomposition of this polymer took place at 301℃. The structure of this polymer is characterized by IR, H2NMR and 13 C2NMR spectra. It's reasonable to conclude that polyphenol with phenol hydroxy groups on the molecular chains are formed through laccase enzymatic polymerization.