We have examined an oxidative coupling of various enzymatically synthesized polyphenols in DMF. Under selected substrate and catalyst concentration, soluble polymers with high molecular weight (M-n > 10(5)) were obtained without formation of insoluble gels. The oxidative coupling behaviors between the precursor polymers and the corresponding phenolic monomers have been compared. The oxidative coupling of some precursor polymers proceeded more efficiently than the direct polymerization of the corresponding monomers. The structure of the starting monomers had a great influence on the oxidative coupling of the precursor polymers. The polymers from o- and m-substituted monophenols were subjected to the efficient oxidative coupling to give high molecular weight polymers quantitatively; on the other hand, the oxidative coupling of the polymers from p-substituted monophenols scarcely proceeded. Polymers from bisphenol and triphenol were also oxidatively polymerized, leading to the quantitative production of the high molecular weight polyphenols under the appropriate reaction conditions.