The electrochemistry of thorium in molten LiF-CaF2 was examined on inert (Mo) and reactive (Ni) electrodes at 1173 K using cyclic voltammetry and chronopotentiometry. A single-step reduction mechanism was observed on the Mo electrode. Voltammetric results show signs of irreversibility. The diffusion coefficient of Th(IV) ions was calculated from the chronopotentiometric data. Deposition of metallic thorium was verified from the electrolytic experiment and subsequent XRD and SEM analyses. The formation of Th-Ni alloys was confirmed on the Ni electrode using cyclic voltammetry, open-circuit chronopotentiometry and SEM + EDS analysis of the deposit after a short electrolysis. (C) 2015 The Electrochemical Society. All rights reserved.