An alternative, biocatalytic approach for the synthesis of a new class of water soluble and processable polyphenols is presented. In this approach, the enzyme horseradish peroxidase (HRP) is used to polymerize phenol in the presence of an ionic template. The template serves as a surfactant that can both emulsify the phenol monomer and growing polyphenol chains and provide water solubility of the final polyphenol/template complex. This approach is a simple, one step synthesis where the reaction conditions are remarkably mild and environmentally compatible. The final product is a water soluble, high molecular weight complex of polyphenol and the template used. The approach is also very versatile as numerous templates may be used to build in specific functionalities to the final polyphenol complex. Polystyrene sulfonates (SPS), lignin sulfonate and dodecyl benzene sulfonates (micelles) are the templates investigated in this study. Thermal analysis and UV-Vis spectroscopy shows that these complexes have exceptional thermal stability and a high degree of backbone conjugation. Electrical conductivities on the order of 10−5 S/cm and third order nonlinear optical susceptibilities (χ(3)) of 10−12 esu are also observed. In the case of the SPS template, under certain conditions, a sol gel complex may be formed. This enzymatic approach offers interesting opportunities in the synthesis and functionalization of a new class of processable polyphenolic materials.