On-site on-demand hydrogen generation from a new Mg-LiBH4-AlCl3 system has been established. The hydrogen yield, mHGR (maximum hydrogen generation rate) and reaction stability can be adjusted by changing the samples' compositions, milling time and water/mixture ratios. The Mg-9 wt.%LiBH4-1 wt.% AlCl3 composite reaches a conversion yield of 87%, corresponding to 1083.5 ml H-2 g(-1) (composite), and the mHGR is 1256.9 ml min(-1) g(-1) in 60 min at 298 K. The synergistic effect between Mg and LiBH4 as well as the catalytic effects of LiBH4-AlCl3 additives both contribute to the improved hydrolytic performances. Compared with the hydrolysis of single Mg or Mg-LiBH4 system, the Mg-LiBH4-AlCl3 mixture has greatly improved its hydrogen yield and mHGR. This mixture is promising for its application as portable hydrogen sources. (C) 2014 Elsevier Ltd. All rights reserved.