Photo-rechargeable batteries are expected to convert solar energy and store it as chemical energy in a single device. Photo-insertion/photo-extraction is the key point for the photo-rechargeable battery but its reaction principle has not been well understood. In this study, we have achieved the reversible photocharge-discharge by constructing the all-solid-state thin film battery with the solid electrolyte. Furthermore, the photo-assisted extraction of Li ions was successfully demonstrated using synchrotron radiation X-ray diffraction measurements.