Catalytic polymerization of catechol was performed employing the cationic porphyrin and horseradish peroxidase (HRP) as catalysts. The obtained results demonstrate that the cationic metalloporphyrin is a more-efficient catalyst than the HRP in the catechol polymerization. The oxidative polymerization was carried out in the presence of polystyrene sulfonate (PSS) as a template. According to TGA data, poly(catechol) that is synthesized by porphyrin catalyst exhibits more thermal stability than the enzymatic catalyzed product. The GPC indicate higher molecular weight of polymer synthesized by porphyrin as a catalyst. Cyclic voltammetry measurements show that the synthesized polymers have convenient electroactivity. The poly(catechol) and its methyl and methoxy derivatives that are synthesized by porphyrin catalyst show low electrical conductivity.