On-demand hydrogen generation from solid-state Al/NaBH4 hydrolysis activated by Li-NiCl2 additives are elaborated in the present paper. Hydrogen generation amount and rate can be regulated by changing Al/NaBH4 weight ratio, Li and NiCl2 amount, hydrolytic temperature, etc. The optimized Al-10 wt.% Li-15 wt.% NiCl2/NaBH4 mixture (weight ratio of 1:1) yields 1778 ml hydrogen/1 g mixture with 100% efficiency within 50 mm at 323 K. The improved hydrolytic performance comes from the effect of Li-NiCl2 additives, which decrease aluminum particle size in the milling process and produce the catalytic promoter BNi2/Al(OH)(3) in the hydrolytic process. Compared with the conventional reaction of Al and NaBH4 in water, there is an interaction of Al/NaBH4 hydrolysis which improves the hydrolytic kinetics of Al/NaBH4 via the catalytic effect of hydrolysis by-products Al(OH)(3), BNi2, and NaBO2. The Al/NaBH4 mixture may be applied as a portable hydrogen generation material. Our experimental data lay a foundation for designing practical hydrogen generators. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.