The direct electro-deoxidation process of solid titanium dioxide was investigated in molten calcium chloride. This study focused on cathodic reactions of the electrolytic process. Products of low-voltage electrolysis were characterized by XRD. The results indicate that titanium dioxide cathode is reduced, although calcium does not exist in molten salt. The current-time plots of the constant voltage electrolysis using different cathodes demonstrate that direct electrochemical reduction of titanium dioxide is the primary reaction in cathodes; at the same time, faint calcium thermal reduction also exists.