The electrochemical behaviour of the Eu(III)/Eu(II) system was examined in the molten eutectic LiF-CaF2 on a molybdenum electrode, using cyclic voltammetry, square wave voltammetry and chronopotentiometry. it was observed that EuF3 is partly reduced into EuF2 at the operating temperatures (1073-1143 K). The electrochemical study allowed to calculate both the equilibrium constant and the formal standard potential of the Eu(III)/Eu(II) system. The reaction is limited by the diffusion of the species in the solution: their diffusion coefficients were calculated at different temperatures and the values obey Arrhenius' law. The second system Eu(II)/Eu takes place out of the electrochemical window on an inert molybdenum electrode, which inhibits the extraction of Eu species from the salt on such a substrate. (c) 2009 Elsevier Ltd. All rights reserved.