A novel biomimetic route for the synthesis of a water-soluble poly(3,4-ethylenedioxithiophene) (PEDT) in the presence of poly(styrene sulfonate) (PSS) and using iron(III)-tetra(p-sulfonatophenyl) porphyrin ((FeTSPP)-T-III), cobalt(III)tetra(p-sulfonatophenyl) porphyrin ((CoTSPP)-T-III), manganese(III)-tetra(p-sulfonatophenyl) porphyrin ((MnTSPP)-T-III), and copper(II)-tetra(p-sulfonatophenyl) porphyrin ((CuTSPP)-T-II) as effective catalysts is presented. The reactions were performed with different monomer, catalyst, template, and initiator concentrations. The absorbance of the polaron bands at various pH values indicated pH 2 as the best condition for polymerization. Precipitation or salting out was highly dependent on the mentioned factors. The formation of PEDT was confirmed by UV-Vis and FT-IR spectroscopy. Cyclic voltammetry proved the convenient electroactivity of the synthesized polymer. The presence of PSS that serves as a charge-compensating dopant provides processability and water solubility and, in addition, a distinct advantage over similar reactions employing native enzymes due to higher stability and lower cost of the catalysts.