Poly (3,4-ethylenedioxythiophene) (PEDOT) nanoporous layers were prepared with electro-oxidative polymerization using room temperature hydrophobic ionic liquids as a medium. The synthesized highly porous PEDOT films exhibit room temperature conductivity value of 195 S cm(-1) along with reproducible high cycling life. These films were used as counter electrodes in dye-sensitized solar cells yielding similar to 8% power conversion efficiency, which is close to the classical platinum coated counter electrode (8.7%). The photovoltaic performance increases as we lower the PEDOT film thickness as the thin films has reasonably high catalytic properties.