The electrochemical behaviour of the systems LiF-NdF3, LiF-Nd2O3 and LiF-NdF3-Nd2O3 was investigated by means of cyclic voltammetry. Neodymium fluorides were reduced, from LiF-NdF3-Nd2O3 melts, via a three-electron reaction to Nd-0 that were deposited on the electrode substrate. Neodymium oxyfluorides were oxidised at anode to oxygen, which was evolved before the oxidation of F-.