An electrochemical method for the direct reduction of solid TiO2 was introduced,in which the oxygen is ionized,dissolved in the molten salt and discharged at the anode,leaving pure titanium at the cathode. Titanium was prepared from TiO2 via molten salt electrolysis,and experimental process was studied in detail. The reductive products of TiO2 were analyzed through XRD,SEM,XPS and so on. The results indicate that titanium with high purity is obtained by the electrochemical reduction. Through thermogravimetric analysis of molten CaCl2,it is shown that the dehydration of CaCl2 has to be strictly controlled to eliminate hydrolysis. The cyclic voltammetry studies on the TiO2 cathode electrochemical system show that the reduction of TiO2 is conducted step by step,from exterior to interior and from high-valence to low-valence. The conclusions were also confirmed by study on thermodynamics analysis. The current efficiency can be improved by loading different voltages in different stages.