TiFe alloy is prepared by the electrolytic reduction of molten-solidified titanium concentrate in molten CaCl2, which is obtained under argon atmosphere. The formation mechanism of TiFe alloy is discussed. The impact of electrolyte time on product is studied when electrolyte voltage is 3.1 V and electrolyte temperature is 900 ℃. Research results show that TiFe alloy with uniform composition can be obtained by this means. The deoxidize product is iron and TiFe alloy by order. The reduction of Ti is a multi-step process and the intermediate products include CaTiO3, TiO2, Ti2O3, TiO, Fe and TiFe2.