In this paper, a novel Al-Bi(OH)(3) system hydrogen-generating material is investigated. Hydrolysis experiments show that the hydrolysis properties of the Al-10 wt% Bi(OH)(3) composite are significantly improved by doping with sodium chloride, and the Al-10 wt% Bi(OH)(3)-5 wt% NaCl composite has a low activation energy (10.4 kJ mol(-1)). With the further optimization of milling time, the hydrogen yield of Al-10 wt% Bi(OH)(3)-5 wt% NaCl composite reaches 1000 mL g(-1) in 1 min. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy and thermogravimetric analysis are applied to characterize the composite and explore the hydrolysis mechanism. The characterization results show that the activation of aluminum mainly comes from three factors: (1) The formation of alumina during ball milling plays an important role in preventing the agglomeration between Al-Bi, Al-Al and Bi-Bi; (2) Bismuth generated during ball milling can form micro-galvanic cell with aluminum to promote the corrosion of aluminum; (3) Sodium chloride as a grinding aid contributes to crush aluminum powder, and chloride ions facilitate the corrosion of aluminum in the hydrolysis process. In addition, the drying method and initial water temperature have a great influence on by-products. The composite is expected to be used in mobile emergency fuel cell due to its rapid hydrogen production capacity. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.