In the present work, the role of NbF5 addition amount in affecting the comprehensive hydrogen storage properties (dehydrogenation, rehydrogenation, cycling performance, hydrogen capacity) of 2LiBH(4)-MgH2 system as well as the catalytic mechanism of NbF5 have been systematically studied. It is found that increasing the addition amount of NbF5 to the 2LiBH(4)-MgH2 system not only results in dehydrogenation temperature reduction and hydriding-dehydriding kinetics enhancement but also leads to the de/rehydrogenation capacity loss. Compared with other samples, 2LiBH(4)-MgH2 doping with NbF5 in weight ratios of 40:4 exhibits superior comprehensive hydrogen storage properties, which can stably release similar to 8.31 wt.% hydrogen within 2.5 h under 4 bar H-2 and absorb similar to 8.79 wt.% hydrogen within 10 min under 65 bar H2 at 400 degrees C even up to 20 cycling. As far as we know, this is the first time that excellent reversibility as high as 20 cycles without obvious degradation tendency in both of hydrogen capacity and reaction rate has been achieved in the 2LiBH(4)-MgH2 system. The further experimental study reveals that the highly catalytic effects of NbF5 on the 2LiBH(4)-MgH2 system are derived from the reaction between NbF5 and LiBH4, which provides a fundamental insight into the catalytic mechanism of NbF5. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.