A Nb-Ti-Ni hydrogen permeable alloy was synthesized as a powder using the OS process, which involves the simultaneous reduction of a mixture of Nb, Ti, and Ni oxides by Ca that is generated from molten CaCl2 via electrolysis. The mechanism confirmed that a BCC-(Nb, Ti) phase easily formed at an early stage of the reaction followed by the generation of a B2-TiNi phase from the lower oxides such as NbO and TiO2. The oxygen content of the synthesized alloy decreased significantly to 0.27 mass% with increased electric charge. The three elements were uniformly distributed at the macroscopic level. (C) 2012 Elsevier Ltd. All rights reserved.