Electrochemical reduction of thionyl chloride has been carried out at glassy carbon and microelectrode that modified by macrocyclic compounds. The catalyst molecules of macrocyclic compounds were adsorbed on the electrode surface and reduced thionyl chloride resulting in a generation of oxidized catalyst molecules. The concentration of catalysts and electrode immersion time were found to affect the catalyst performance strongly. Significant improvements in cell performance have been noted in terms of both exchange rate constants of up to 10 times and power densities of up to 220% at glassy carbon electrode. The diffusion coefficients obtained at carbon microelectrode were slightly different from that determined at glassy carbon electrode.