The photovoltaic performances of dye-sensitized solar cells employing solid polymer electrolytes have been greatly improved by the introduction of a chemically doped (p-type) conjugated polymer junction layer onto a conventional platinum-layered counter electrode. The increased energy conversion efficiency would be primarily due to the decrease in the interfacial charge-transfer resistances between the polymer electrolyte and the Pt-layered counter electrode, as confirmed by the results of FE-SEM and impedance spectroscopy.