Solid-oxide-oxygen-ion conducting membrane (SOM) process is a novel, high efficient, low cost, energy-saving, environmentally friendly electrochemical extraction method of metals or alloys. This work demonstrated the prototype development of preparation of hydrogen storage alloys by SOM process, and Ti-Fe based quaternary alloy was successfully prepared directly from the oxides in molten calcium chloride. The assembling process of electrode utilized in the recycled battery was extended to prepare the novel cathode, it proved that this design can effectively simplify the assembly process and dissolve the problem of incomplete electrolysis. It is shown that SOM electro-deoxidization process was faster and more efficient for the current, the as-prepared alloy showed a good stability in the charging/discharging cycles and the capacity reached 27.88 mAh g(-1) after ten activated cycles. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.