A novel composition of AlLi/NaBH4 mixture activated by common Ni powder in water for hydrogen generation was investigated. The composition presents good hydrogen generation performance and an optimized Al-10% Li-10% Ni/NaBH4 mixture (mass ratio of 3:1) generates 1540 mL/g hydrogen with 96% efficiency at 333 K. Ni powder exhibits dual catalytic effects on the hydrolysis of AlLi/NaBH4 mixture due to the formation of Ni2B in the hydrolysis process. The Ni2B deposited on aluminum surface could act as a cathode of a micro galvanic couple. Ni2B/Al(OH)3 also has a synergistic effect on NaBH4 hydrolysis. Good hydrogen generation performance with stable pH value of hydrolysis byproduct Al(OH)3/NaBO2-2H2O was obtained with successive additions of Al-Li-Ni /NaBH4 mixture into fixed water.