Abstract: TiFe alloy was prepared directly by electrolytic reduction from the mixture of TiO₂ and Fe₂O₃ in molten CaCl₂ at 1173 K and 3.1 V. The reduced product was TiFe with an oxygen content of 0.43% in mass fraction after electrolyzing for 10 h. The whole electrolysis process, roughly, includes two periods:the reduction of Fe element and the forming of TiFe. In the initial stage of electrolysis, Fe element is reduced first prior to titanium and CaTiO₃ is formed. Then the external cathode is reduced to TiFe. Meanwhile, the cathode is layered:the external loose layer mainly contains TiFe and the inner layer, which is much harder and more compact, chiefly consists of Fe and CaTiO₃. Electrochemical behavior test shows that the discharge capacity of TiFe alloy produced by electrolysis without activation is about 33 mA·h·g^-1 and TiFe alloy by this performance is better than those prepared by other methods.