Electrochemical redox behaviour of Ce (III) ion in LiF-CaF2 eutectic was studied at 1093 K using tungsten (inert) and nickel (reactive) as working electrodes and platinum as quasi-reference electrode by various electrochemical transient techniques viz, cyclic voltammetry (CV), square-wave voltammetry (SQWV) and chronopotentiometry (CP). It was deduced that reduction of Ce (III) to Ce metal occurs by a single step, three-electron transfer. Diffusion coefficient (D-Ce(III)) of Ce (III) ion was determined from CV, semi-integral analysis and CP and the values obtained were 2.2 x 10(-5), 5.4 x 10(-5) and 3.0 x 10(-5) cm(2) s(-1), respectively. Electrochemical studies in the presence of Ni electrode showed the formation of the inter-metallic compounds CeNi5 and Ce2Ni7, which were characterized by powder X-ray diffraction and SEM-EDAX analysis. (C) 2011 Elsevier Ltd. All rights reserved.