In this article, described are our recent advances in enzymatic polymerization, defined as chemical polymer syntheses in vitro (in test tubes)via non-biosynthetic pathways catalyzed by an isolated enzyme. The major target macromolecules formed via the enzymatic polymerizations in this article are polyesters and polyphenols. For synthesis of polyesters, hydrolases are used as catalyst; hydrolases, enzymes catalyzing a bond-cleavage reaction by water, induce the reverse reaction of hydrolysis, leading to polymer production by a bond-forming reaction. Specific enzyme catalysis provides a novel synthetic route for useful polyesters, many of which are difficult to be synthesized by conventional methodologies. Peroxidase and laccase act as catalyst for oxidative polymerization of various phenol derivatives to produce a new class of phenolic polymers without use of toxic formaldehyde under mild reaction conditions. Artificial urushi has been developed by laccase-catalyzed curing of new urushiol analogues