Nanocomposite films with interconnected pores are fabricated using TiO2 as porous template with poly 3,4-ethylenedioxythiophene:polystyrene sulfonate (PEDOTPSS) as catalyst, and then are developed as alternative counter electrodes for dye-sensitized solar cells (DSC). The porous templates are prepared by depositing the TiO2 nanoparticles on the conductive SnO2 transpanent glass doping fluorine (FTO), followed by annealing. The nanocomposite films are then completed by spin coating of the commercial PEDOTPSS aqueous solution into the template. By optimizing the template structures and the spin coating rates, the nanocomposite film with excellent catalytic activity for the tri-iodide reduction is obtained. When employing this nanocomposite film as the counter electrode for the DSC, the optimum fill factor and efficiency respectively reach to 0.528 and 4.57%, which are greatly higher than those of the cells with the pure PEDOTPSS film as the counter electrode. The fill factor and efficiency of the latter are 0.297 and 1.98%, respectively. The improved photovoltaic performances are attributed to the excellent synergistic effects of the nanocomposite film. The conducting TiO2 skeleton provides high-speed conductive paths for the electrons transportation, and the PEDOTPSS adhered on the skeleton engenders large surface area provides more active sites for the tri-iodide reduction.