Fine magnetic powder of a terbium-iron intermetallic compound, TbFe2, was prepared by electrochemical reduction of thermally compounded powders of Tb4O7 and Fe2O3 (atomic Tb/Fe ratio, 1:2) in molten CaCl2. The electro-reduction potential of mixed Tb4O7 and Fe2O3 powders was more positive than that of Ca2+ in molten CaCl2 as revealed by cyclic voltammetry using a novel metallic cavity electrode. Porous pellets of mixed Tb4O7 and Fe2O3 powders were prepared by sititering in air, and were reduced to various Tb-Fe intermetallic compounds by constant voltage electrolysis at typically 2.6-3.2 V and 900 degrees C for 10-12 h. The electrolytic product could be cleaned effectively in dimethylsulfoxide under magnetic stirring, leading to a pure magnetic powder with a low oxygen content (< 1300 ppm) and the desired TbFe2, stoichiometry as confirmed by XRD and ICP-AAS. It was also found that raising the sintering temperature (1200 degrees C, 2 h) encouraged compound formation between Tb4O7 and Fe2O3 powders and led to better stoichiometry control ill the electrolytic product. Energy consumption of the electrolysis could be lower than 14 kWh/kg TbFe2, and the Tb recovery yield reached beyond 97%. (c) 2006 Elsevier B.V. All rights reserved.