By using NH₄VO₃ as raw material, high-active V₂O₃ cathode pellets were prepared by reduction with coal gas and in-situ sintering, then were directly reduced to metallic vanadium by rapid electro-deoxidization in molten fluorides. The mechanism of V₂O₃ electro-deoxidization was studied by cyclic voltammetry experiments and constant potential electrolysis experiments. The results indicate that the rapid electro-deoxidization of V₂O₃ can be realized in molten fluorides, metallic vanadium containing 0.218 wt% oxygen can be obtained after 4 h electrolysis. The in-suit formation of aluminium-oxygen-fluorine complex ions, which further forming aluminum metal in deoxidation reaction zone, caused aluminum thermal reduction reaction of V₂O₃ cathode. So direct electro-deoxidation reduction and aluminum thermal reaction of V₂O₃ both existed in the deoxidation process of V₂O₃ cathode, and the latter reaction played a key role in acceleration action. Electro-deoxidization process of V₂O₃ cathode can be enhanced effectively by adding aluminium oxide in molten fluorides, the electrolytic time can be shortened to 3 h with other conditions unchanged.