Poly (3,4-ethylenedioxythiophene) (PEDOT) polymers with different electric conductivities were synthesized directly on a FTO substrate via a chemical polymerization method and applied as a platinum (Pt)-free counter electrode for dye-sensitized solar cells (DSSCs). The catalytic properties of the PEDOT as a function of electrical conductivity were studied using cyclic voltammograms, J-V measurements and impedance spectroscopy. The PEDOT counter electrode with around 340 S/cm conductivity exhibited the best performance as a counter electrode for tri-iodide reduction. The ability to modulate catalytic activity of PEDOT with changes in conductivity shows one of promising routes for developing new counter electrode of Pt-free DSSCs.