Al–10Bi–7Zn and Al–10Bi–7Zn–1.5X (X: Cu, Fe, Ni, in wt.%) composite powders were designed and prepared through phase diagram calculation and gas atomization method. The effects of Cu, Fe, and Ni on the hydrolysis of Al–Bi–Zn-base composite powders for hydrogen production were investigated respectively. The composition and morphology of powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy disperse spectroscopy (EDS) analyses. Hydrolysis performance test results indicate that the additions of Cu, Fe, or Ni can modify the hydrogen production rate and enhance oxidation resistance in Al–10Bi–7Zn ternary alloy composite powder. In the quaternary composite powder system, Al–10Bi–7Zn–1.5Ni (wt.%) exhibits the best performance with the hydrogen generation yield of 75.3% (954.1 mL/g) within 500 min when reacting with distilled water at 60 °C and maintains a hydrogen yield of 57.9% (733.7 mL/g) within 1500 min after being stored (30 °C, relative humidity of 60%) for 7 d. In addition, the mechanism investigation suggested that the additions of Cu, Fe, or Ni in Al–Bi–Zn-base composite powders can stabilize the Al matrix to retain the high activity of powders resulting from inhibiting the cracking of composite powders in the air.