Abstract Ti2CrV alloy shows good hydrogen storage characteristics at room temperature and ambient pressure. The present study investigated the feasibility of direct electrochemical reduction of TiO2-Cr2O3-V3O5 to Ti2CrV in CaCl2 melt at 900oC by the FFC Cambridge process. The electrolysis was conducted in a two-electrode assembly with the sintered mixed oxide cathode and HD graphite anode at a constant cell voltage of 3.1 V for different time intervals to elucidate the reduction mechanism of the metal oxide mixture. The obtained products were characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. Cyclic voltammetry studies using metallic cavity electrode containing mixed metal oxide powder were also carried out to determine the electrochemical reduction behavior in CaCl2 melt at 900oC. It was observed that the presence of pre-formed Cr and V metal in the vicinity of titanium oxide helped in its faster reduction. The complete metallization of the sintered mixed oxide pellet occurred after 15 h of electrolysis. The electrochemical reduction mechanism was observed to proceed through various intermediates such as chromium-rich Cr-V, vanadium-rich V-Cr, CaTiO3, TiO, Ti6O, Ti-V, and C15-TiCr2.