TiFe alloys were prepared by ilmenite electrolysis in CaCl2 molten salt, and the reaction progress of the electrolysis was investigated. The composition of the electrolytic products and the electrolytic efficiency were analyzed. Results show that the reduction of ilmenite undergoes an alloying course of prior formation of Fe and gradual formation of TiFe2 and TiFe. The in-process products include CaTiO3, Fe2TiO4 and TiO. The alloy firstly formed in the reaction is TiFe2, and then it converts into TiFe alloy by the interdiffusion between Ti and TiFe2, indicating the diffusion is a control step of the reaction. Under the same electrolysis condition, ilmenite is more difficult to electrolyze than the mixed oxides. It is because that those ilmenite particles are big and the impurity is solid solutioned into the iron titanate, so deoxygenation is more difficult and the electrolytic efficiency is much lower