A photo-rechargeable supercapacitor (photo-supercapacitor, or PSC) is studied using a N3-dye adsorbed TiO2 photoelectrode and PProDOT-Et2 poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepine) polymer films as supercapacitor materials for electron storage. The PSC device, comprising a dye-sensitized solar cell (DSSC) and a supercapacitor (SC), can store the photo-to-electric energy. The PProDOT-Et2 films are potentiostatically electropolymerized to form thick films (ca. 0.5mm) with a specific capacitance of ca. 6.5Fcm−2. A symmetrical (p/p) supercapacitor, with PProDOT-Et2 coated on both electrodes, is also characterized before fabricating the three-electrode PSC. The PSC is tested under light illumination of 100mWcm−2, and attaining a photocharged voltage of 0.75V and a discharged energy density of 21.3μWhcm−2.