A new process is studied to synthesize the hydrogen storage alloy directly from its oxides. This method combines the calcium co-reduction and the in situ dissolution of the by-product CaO into the molten salt. The binary alloy of 30 mol percent Ti-70 mol percent V was chosen as an example. When V2O5 and TiO2 were used as the starting materials, the reduction and alloying occurred separately in part, because V2O5 was melted below the reaction temperature and the preferentially reduced metallic V droplets deposited on TiO2 powder, which hindered the reduction of TiO2. The well-homogenized alloy could be obtained from the mechanical mixture of refractive V2O3 and TiO2. The molten CaCl2 was needed to dissolve CaO for complete reaction. The obtained alloy powder showed capability of hydrogen storage after activation.