The concept of a novel electrochemical reduction process for the treatment of spent nuclear fuels in Li2O-LiCl molten salt was proposed and fresh tests using U3O8 powder were carried out to elucidate the reaction mechanism and verify the feasibility of the process. Electrolysis of Li2O and reduction of U3O8 powder took place simultaneously at the cathode part of the electrolysis cell via a catalytic EC mechanism and the conversion of U3O8 to U metal was more than 99%.