Abstract: The equilibrium composition of V₂O₅ and reductant during direct alloying of V₂O₅ as a complex system composed of muti-component and multi-phase were simulated by HSC and then analyzed.The result of thermodynamic calculation shows that the reduced products of V₂O₅ carbothermic reduction is the carbide of vanadium,the system of silicothermic reduction should add CaO,aluminothermic reduction can reach a reduction rate of 99%,the reduction ability of Al is more effective than that of C and Si.The complex silicothermic and aluminothermic reduction can reach a high reduction rate by using a small quantity of Al,the calculation result is consistent with the thermodynamic law of the industrial practice of making ferrovanadium by electricity -silicothermic method.