Titanium oxycarbide (TiCxOy) was successfully prepared by an electro-deoxidation of TiO2/C composite cathode in molten calcium chloride at 900 degrees C. The composite cathode was prepared by adding an amount of carbon into TiO2 powders. By using X-rays diffraction and scanning electron microscopy, it was found that the presence of carbon resulted in changes in reaction mechanism and accelerated the rate of electrochemical reaction. The results suggested that the electrochemical reduction of TiO2/C composite was the following: firstly titanium dioxide was reduced to TiOn (0 < n < 1) along with the formation of CaTiO3. Then, TiOn (0 < n < 1) reacted with carbon to TiCxOy. (C) 2012 Elsevier Ltd. All rights reserved.