The electro-deoxidation of V₂O₃ precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl₂ and NaCl with additions of CaO, a cathode of compact V₂O₃, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). 3 g of V₂O₃ could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V₂O₃ formed the intermediate product CaV₂O₄.