The CaTiO3 compounds were prepared by sintering the mixtures of the TiO2 and CaO in air. The compounds were used as cathode, the graphite as anode and the molten CaCl2-NaCl as electrolyte. Electrolysis was performed at 800°C and constant-voltage 3.2V in dry argon atmosphere. The results showed that the electrolytic rate could be significantly enhanced because of the additive CaO. The electrolysis time was shortened efficiently than that of direct electrochemical reduction of solid TiO2.