A novel and environmentally friendly route to directly prepare metallic vanadium from NaVO3 by molten salt electrolysis is proposed. The feasibility about the direct electro-reduction of NaVO3 to metallic vanadium is analyzed based on the thermodynamic calculations and experimental verifications. The theoretical decomposition voltage of NaVO3 to metallic vanadium is only 0.47 V at 800 degrees C and much lower than that of the alkali and alkali earth metal chloride salts. The value is slightly higher than that of low-valence vanadium oxides such as V2O3, V3O5 and VO. However, the low-valence vanadium oxides can be further electro-reduced to metallic vanadium thermodynamically. The thermodynamic analysis is verified by the experimental results. The direct preparation of metallic vanadium from NaVO3 by molten salt electrolysis is feasible. (C) 2016 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.