A novel hydrogen generation material with a high capacity of H₂ release had been successfully prepared by ball milling both NaMgH₃ and Al powder. The performances of H₂ generation of the material and effects of metals, salts or complex hydrides on this material are explored. The action mechanism of NaMgH₃, Bi and Li₃AlH₆ on Al-H₂O reaction is investigated by means of XRD and calorimeter. The results show that doping only NaMgH₃ into Al powder can induce a reaction of Al-NaMgH₃ composite with water to release H₂, but its yield is only 42.9% at 298.15 K. Because of forming of a layer MgAl₂(OH)₈ on the surface of the Al particles, it leads to Al could not constantly contact with water. The experimental result find that doped Bi can accelerate the rate of H₂ generation while doped Li₃AlH₆ contributes to enhance the yield of H₂. By doping simultaneously Bi and Li₃AlH₆, the amount of H₂ generation and the yield of Al-NaMgH₃-Bi-Li₃AlH₆ increase to 1379.8 mL/g and 100% at 298.15 K, respectively.