There has been much interest in polymerization catalyzed by enzymes (“enzymatic polymerization”) as a 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 a complicated structure,which is hard to synthesize by conventional oxidative polymerizations．As a p-diphenol 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 (pH 4) and organic (15:85,vol％) catalyzed by a laccase,produced from white rot fungus,at 35℃ for 48 h to form a polymer,2,6-poly (4-phenylphenol) 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 168.84℃ and the decomposition of this polymer took place at 301℃．The structure of this polymer is characterized by IR,H-NMR and 13C-NMR spectra．It’s reasonable to conclude that polyphenol with phenol hydroxy groups on the molecular chains are formed through laccase enzymatic polymerization．