In this paper, we reported on the electrochemical reduction of SiO 2 using LiCl–Li 2O molten salt as an electrolyte. Feed material, SiO 2 powder, contained in a porous magnesia basket was charged into an electrolysis cell and made as a cathode. Reduction in LiCl–Li 2O molten salt allowed for a much lower reaction temperature compared to the electrochemical reduction in molten CaCl 2. Li metal production via electrolysis of Li 2O and reduction of SiO 2 took place simultaneously inside the cathode basket of an electrolysis cell. Analysis of the time-dependent changes of a phase composition showed that the reduction proceeded through Li 2SiO 3. This new silicon preparation technique was compared with the conventional deoxidation methods reported in the literature.