An investigation into the electrochemical reduction of TiO2 to Ti in molten LiCl-Li2O has been performed. Analysis of the time-dependent changes of a phase composition shows that the reduction proceeds through lithium-containing intermediates consisting of LiTi2O4 and LiTiO2. The reduction of TiO2 in molten LiCl-Li2O allows a much lower reaction temperature compared to the conventional reduction process in molten CaCl2.