A new process to obtain hydrogen from highly activated Al-Li-Bi alloys in water is described. The alloys had good hydrolytic properties at 298 K, and the optimized composite yielded 1340 mL hydrogen/g Al with 100% efficiency and achieved a maximum hydrogen generation rate of 988 mL/min g Al. These values are much higher than those obtained from hydrogen production with pure Al under the same conditions. The improvements were brought about by the increased amount of Li in the alloys: Al alloys with higher Li contents have larger surface areas and smaller grain sizes, allowing more hydrogen to be generated from Li hydrolysis in water. XRD and SEM analyses showed that the formation of BiLi(3) was helpful in improving the hydrolytic properties of the alloys via the work of the micro galvanic cell between Al and Bi, which was stimulated by the LiOH solution obtained from Li hydrolysis in water. Other effects, such as Bi content, global temperature, and annealing conditions, were also discussed. Al-Li-Bi alloys show promise as potential materials for supplying portable hydrogen to fuel cells. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.