TiV alloys were prepared by electro-deoxidization method. Using molten CaCl2 as electrolyte, mixed oxides of sintered V2O5 and TiO2 as cathode, and graphite rod as anode, the samples were electrolyzed at 900 ℃ under 3.0-3.2 V. The electrolysis principle was studied. Results show the reaction process is gradual reduction of mixed oxides to produce content-controllable TiV alloys. The process is prior production of Ti subsequent to gradual production of TiV alloy. The intermediate products include CaTiO3, V4O9 and TiO et al.