Energy output by the solar-electric energy conversion which achieved by the dye sensitized solar cells (DSC) is greatly influenced by luminance depending on weather, time, and so on. Photocapacitor which combined DSC and electric double layer capacitor (EDLC) is the novel device having photoelectric generation and electric charge-discharge abilities, and it expected to improve the problems about steady electric power supplements by the solar energy conversion. We have first construct a high-voltage photocapacitor of three-electrode configuration, comprising a dye-sensitized mesoporous TiO₂ electrode, two carbon-coated electrodes, and two liquid electrolytes. The three-electrode system attained a charge-state voltage of 0.8V and drastically high energy density compared with the previous two-electrode photocapacitor.