Doping Mg(NH2)(2)-2LiH by Mg-2(BH4)(2)(NH2)(2) compound exhibits enhanced hydrogen de/re-hydrogenation performance. The peak width in temperature-programmed desorption (TPD) profile for the Mg(NH2)(2)-2LiH-0.1Mg(2)(BH4)(2)(NH2)(2) was remarkably shrunk by 60 degrees C from that of pristine Mg(NH2)(2)-2LiH, and the peak temperature was lowered by 12 degrees C from the latter. Its isothermal dehydrogenation rate was greatly improved by five times from the latter at 200 degrees C. XRD, FTIR and NMR analyses revealed that a series of reactions occurred in the dehydrogenation of the composite. The prior interaction between LiH and Mg-B-N-H yielded intermediate LiBH4, which subsequently reacted with Mg(NH2)(2) and LiH in molar ratio of 1:6:9 to form Li2Mg2(NH)(3) and Li4BN3H10 phases. The observed 6Mg(NH2)(2)-9LiH-LiBH4 combination dominated the hydrogen release and soak in the composite system, and enhanced the kinetics of the system. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.