Vanadium slag contains several critical elements like V, Ti, Cr, Fe and Mn. In our previous work, V and Cr have been enriched by selective chlorination, increasing from 10.05% to 14.95% and 5.84%-8.69% separately. V and Cr still maintain the trivalence state in molten salt. In the current work, the electrodeposition behaviors of V3+ and Cr3+ in NaCl-KCl molten salt at 800 degrees C were investigated using cyclic voltammetry (CV) and square wave voltammetry (SWV) with a tungsten electrode. It was found that the reduction processes of V3+ and Cr3+ consist of two steps, M3+/M2+, M2+/M. The diffusion coefficients of V3+ and Cr3+ in NaCl-KCl molten salt were measured by CV. The effect of VCl3/CrCl3 mass ratio on VCr alloy was investigated by a two-electrode under constant voltage. Pure Cr can be obtained at 2.8 V in the NaCl-KCl molten salt, while VCr alloy (3.71 mass % V-94.28 mass% Cr-2.01 mass % O) was obtained when electrolysis voltage was controlled to 2.8 V at 800 degrees C. The composition of VCr alloy can be designed by changing the molten salt composition. This method can be applied for direct preparation of VCr alloy from vanadium slag, thus offering the use of low cost raw materials with direct environmental benefits. (C) 2019 Published by Elsevier B.V.