A new conducting polymer poly (3, 4-phenylenedioxythiophene) is synthesized by the electrochemical polymerization technique with different solvents. We find that solvents used in electrochemical polymerization play important roles for the catalytic activity and morphology of the formed conducting polymers. The obtained poly (3, 4-phenylenedioxythiophene) is for the first time employed as counter electrode electrocatalyst in dye sensitized solar cells with cobalt-based electrolytes. We demonstrate that a polymer prepared from a mixed acetonitrile-dichloromethane solvent exhibit higher catalytic activity for redox reactions, as compared to that from a single solvent, dichloromethane. The devices based on this mixed solvent-based polymer from a mixed solvents show a high power conversion efficiency of 5.97%. An additional advantageous feature of the electrochemically polymerized poly (3, 4-phenylenedioxythiophene) for solar cell applications is the high transparency in the visible and nearinfrared region. We also investigate the beneficial effect of the poly (3, 4-phenylenedioxythiophene) layer thickness on device performance, and concluded that the series resistance and charge transfer resistance are greatly influenced by the thickness of polymer, as evidenced by electrochemical impedance spectroscopy measurements. The optimal thickness for poly (3, 4-phenylenedioxythiophene) is about 100 nm. Furthermore, the high catalytic activity and transparency of the new conducting polymer as counter electrode shows great promise for other optoelectronic applications. (C) 2019 Published by Elsevier Ltd.