The most advanced methodology for the pyroprocessing of spent nuclear fuel is the electrorefining of uranium metal in LiCl-KCl eutectic, in which uranium is solubilized as U(III). The production of U(III) in LiCl-KCl eutectic by the chlorination of uranium metal using BiCl3 in has been performed for research purposes. In this work, this reaction was studied in-situ by visual observation, electronic absorption spectroscopy and electrochemistry at 450 °C. The most likely mechanism has been determined to involve the initial direct oxidation of uranium metal by Bi(III) to U(IV). The dissolved U(IV) then reacts with unreacted uranium metal to form U(III).