Enhanced dehydrogenation properties for ammine lithium borohydride (LiBH4 center dot NH3) melt-infiltrated into Al2O3 nanoscaffolds are reported. X-ray diffraction measurements verified the formation of intermediate phase of amorphous state during heating the composites at 65 degrees C. Subsequently, it was revealed by combination of gravimetric and volumetric measurements that a hydrogen desorption capacity of 12.8 wt.%, accounting for 91 mol% of the total amount of the released gas at 230 degrees C, was achieved for the LiBH4 center dot NH3/Al2O3 composite with a mass ratio of 1:4, while in the pristine LiBH4 center dot NH3 merely trace amount of H-2 was detected at this temperature. Moreover, Fourier transform infrared spectra and B-11 nuclear magnetic resonance spectra were combined to clarify the facilitated recombination of NH3 groups and BH4-1 anions in the composites. As a consequence, the mechanisms for the promoted dehydrogenation in the composites were reasonably deduced as twofold, firstly, the nanosize effects of the loaded LiBH4 center dot NH3 on the dehydrogenation properties in the presence of the oxide nanoscaffolds, which serve as the highly dispersing support for the loaded materials, and assist the formation of the amorphous phase during heating; secondly, the impact of Al2O3 nanoscaffolds on the dehydrogenation of the loaded materials, via promotion of the recombination between BH and NH groups. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.