The electrochemical behaviourof the Nd(III)/Nd(0) system has been investigated in several molten media and more particularly in LiF-CaF2. preliminary study based both on thermodynamic and experimental data showed that it is not possible to observe the Nd(III)/Nd(0) system in LiF-KF and LiF-NaF melts; because the K+ and Na+ cation reduction waves hide the Nd3+ reduction wave. Then, the Nd(III)/Nd(0) system has been investigated at 810degreesC using solutions of NdF3 in fluoride solvents without K+ and Na+` ions, such as LiF-CaF2, by cyclic voltammetry, chronopotentiometry and square wave voltammetry. Experimental results show that neodymium trifluoride is reduced in Nd(0) in a one-step process exchanging three electrons (Nd(III) + 3e(-) --> Nd(0)). The electrode process is shown to be diffusion controlled. Nd(Ill) diffusion coefficient is in the range of 1.1-1.3 x 10(-5) cm(2) s(-1) at 810degreesC. (C) 2004 Elsevier Ltd. All rights reserved.