Solar cell performances of the cosensitized dye-sensitized solar cells (DSCs) with Black dye and D131 using the electrolyte solution containing a quaternary phosphonium iodide with a various alkyl chain length have been evaluated by the photoelectrochemical and the electrochemical impedance spectroscopic measurements. Effects of the difference of the central atom between the quaternary phosphonium iodide and the quaternary ammonium iodide on the solar cell performances have been clarified. The DSC using the electrolyte solution containing tetrabutylphosphonium iodide showed higher Jsc. value and lower Voc and FF values compared to those of the DSC using the electrolyte solution containing tetrabutylammonium iodide. In addition, effects of the alkyl chain length of the quaternary phosphonium iodide on the solar cell performances have been also investigated. The blocking effect of the quaternary phosphonium cation for the access of I-3 to the TiO2 surface was found to be improved with increasing the alkyl chain length. The highest conversion efficiency (11.3%) could be obtained in the cosensitized DSC with Black dye and D131 using the electrolyte solution containing a moderate concentration of tetraoctylphosphonium iodide under AM 1.5 (100 mW/cm(2)) irradiation. This study demonstrated that the quaternary phosphonium iodide with a longer alkyl chain is also effective for the improvement of the conversion efficiency of the DSCs due to both the improvement of the electron lifetime in the TiO2 photoelectrode and the slight increment of the conduction band energy of the TiO2. (C) 2015 Elsevier Ltd. All rights reserved.