Abstract: TiW alloy with high W content was prepared directly by electrolysis in molten-salt from the mixture electrode of TiO₂ and WO₃,and the current change,phase component and microstructure evolvement were studied and analyzed.Under the electrolysis conditions of 900℃ and 3.1 V voltage,with a graphite anode and TiO₂-WO₃ oxides cathode,the electrolysis was carried out in molten CaCl₂ salt,and the electrolysis products were examined by SEM,EDS and XRD during the process.The TiW alloy with uniform component was obtained after electrochemical reduction,where the atomic ratio of Ti and W of produced alloy was agreed closely with the pre-determined ratio,and the reduced products had low oxygen content after electrolyzing for 16h.