AbstractA method for obtaining hydrogen through the hydrolytic reaction of highly activated aluminum (Al) alloy is investigated. The optimized Al–3 wt.% Li–4 wt.% In–7 wt.% Zn alloy significantly improves the maximum hydrogen generation rate and amount (137 mL g–1 min–1 and 1,243 mL g–1, respectively). An efficiency of 100% was reached within 1 h at 298 K. The synergistic catalytic effects of Li, In, and Zn, which stimulated Al hydrolysis through the formation of micro galvanic cells of In–Li and Al–In–Zn alloys in water, were observed. The reactions were analyzed using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and hydrolytic experiments. The In–Li alloy functions as an initial active center and produces LiOH in water, which further stimulates and changes the hydrolytic process of the Al–In–Zn alloy. The effects of alloy composition, milling time, and hydrolytic temperature were considered and discussed. The results indicate that the hydrolytic reaction of Al–Li–In–Zn alloy in water might be feasible for the production of inexpensive, pure, and safe hydrogen for micro fuel cells.