A solid-state photoelectrochemical cell is operated between 400 and 500 degrees C under 365 nm UV light. The cell consists of a photovoltaic part, based on a La0.8Sr0.2CrO3/SrTiO3 junction, and an electrochemical part including a zirconia solid electrolyte with a shared (La,Sr)FeO3 electrode. The photovoltaic cell part leads to open circuit voltages up to 920 mV at 400 degrees C. Upon UV light, this driving force is used in the electrochemical part of the cell to pump oxygen from low to high partial pressures, i.e., to convert radiation energy to chemical energy. This demonstrates the feasibility of high-temperature photoelectrochemical cells for solar energy storage. The detailed characterization of the different resistance contributions in the system by DC and AC methods reveals the parts of the cell to be optimized for finally achieving high-temperature photoelectrochemical water splitting.