The effects of basicity and MgO content on reduction behavior and separation of iron and slag during smelting vanadium titanomagnetite by electric furnace were investigated. The reduction behaviors affect the separation of iron and slag in the direct reduction-electric furnace process. The recovery rates of Fe, V, and Ti grades in iron were analyzed to determine the effects of basicity and MgO content on the reduction of iron oxides, vanadium oxides, and titanium oxides. The chemical compositions of vanadium-bearing iron and main phases of titanium slag were detected by XRF and XRD, respectively. The results show that the higher level of basicity is beneficial to the reduction ofiron oxides and vanadium oxides, and titanium content dropped in molten iron with the increasing basicity. As the content of MgO increased, the recovery rate of Fe increased slightly but the recovery rate of V increased considerably. The grades of Ti in molten iron were at a low level without significant change when MgO content was below 11%, but increased as MgO content increased to 12.75%. The optimum conditions for smelting vanadium titanomagnetite were about 11.38% content of MgO and quaternary basicity was about 1.10. The product, vanadium-bearing iron, can be applied in the converter steelmaking process, and titanium slag containing 50.34% TiO₂ can be used by the acid leaching method.