Al-Bi-NaCl composites was prepared by ball milling. Firstly, Al-5%Bi-10%NaCl was used as the research object to study the effect of milling time on the hydrogen production performance of Al-5%Bi-10% NaCl composites. Then, the content of Bi and NaCl was changed appropriately to carry out the ball milling experiment. The influence of the content of Bi and NaCl on the hydrogen generation performance was investigated. Finally, the Al-4%Bi-4%NaCl composites with the highest hydrogen production efficiency was obtained under the milling parameters of milling time of 11h, milling speed of 360r/min and ball-to-material ratio of 10:1. The hydrogen yield of composites material was 1156 ml/g in 1 h. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were used to analyse the phase, morphology and element distribution of the composites. The results show that there is no new phase formation in the ball milling process. Al, Bi, and NaCl are only mechanically mixed. The Bi is uniformly distributed in the composites material. The corrosion effect of the micro-cell generated between Al-Bi is the key to promote the reaction of Al with water.