In this article tetrabutylammonium bromide(TBAB) was first added in buffer to compose a convenient and environmentally friendly system, and enzymatic polymerization of phenol catalyzed by horseradish peroxidase(HRP) could proceed efficiently in this system. When TBAB was added, the most conversion of phenol could reach 99.1%. The phenol polymer was considered to consist of a mixture of phenylene(Ph) and oxyphenylene(Ox) units by IR analysis, and the ratio of phenylene to oxyphenylene units(Ph/Ox) was measured by titration. Moreover, the effects of the dosage of horseradish peroxidase(HRP) and pH value on the conversion of phenol were investigated. The reaction performed very effectively in this novel system when the addition of HRP was only 0.2 mg. In all cases, the weight-average molecular weight calculated by GPC-SLS was in a range from 12000 Da to 30000 Da. The phenol polymer prepared in the present research possessed good thermal stability shown by TG analysis. In this article tetrabutylammonium bromide (TBAB) was first added in buffer to compose a convenient and environmentally friendly system, and enzymatic polymerization of phenol catalyzed by horseradish peroxidase (HRP) could proceed efficiently in this system. When TBAB was added, the most conversion of Phenol could reach 99.1%. The phenol polymer was considered to consist of a mixture of phenylene (Ph) and oxyphenylene (Ox) units by IR analysis, and the ratio of phenylene to oxyphenylene units (Ph / Ox) was measured by titration. The effects of the dosage of horseradish peroxidase (HRP) and pH value on the conversion of phenol were investigated. The reaction performed very effectively in this novel system when the addition of HRP was only 0.2 mg. In all cases, the weight-average molecular weight calculated by GPC-SLS was in a range from 12000 Da to 30000 Da. The phenol polymer prepared in the present research possessed good thermal stability shown by TG analysis.