The electro-deoxidation method was used to reduce the sintered bulk TiO2 doped with CaCO3 (as cathode) to titanium in CaCl2 melt at 900°C. The morphology and composition of TiO2 cathode, the impact of CaCO3 doping in on TiO2 cathode were investigated. The results show that CaCO3 doping in TiO2 cathode will increase the porosity of the sintered solid TiO2, affect the particle size of TiO2 and benefit the increase of the cathode electrolysis reaction speed as well as rise the efficiency of electrochemical reduction.