The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO2 reduction is considered in this study. Present work clarifies, by electroanalytical techniques, the reduction pathway leading to the metal. The reduction of CeO2 into metal was feasible via an indirect mechanism. Electrolyses on lOg of CeO2 were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl2-KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride. (C) 2011 Elsevier Ltd. All rights reserved.