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The mutual destabilization between complex hydrides and lithium amide has been comprehensively reported. In this paper, CeH2 doped Li-Mg-N-H/NaA1H4 composite was successfully synthesized by ball milling Li-Mg-N-H mixture and NaA1H4 in a molar ratio of 1:2. It was found that a total of 5 wt.% of hydrogen could be desorbed from the newly synthesized composite with a three-step reaction. Temperature-programmed-desorption (TPD) measurements showed that the composite ball milled for 10 min began to desorb hydrogen below 100 ℃,which was about 75 ℃ lower than the pristine materials. XRD analysis revealed that NaAlH4 firstly reacted with LiH to yield Na2LiAlH6 and A1 below 150 ℃, then the newly developed Na2LiAlH6 reacted with Mg(NH2)2 to form NaiH, Al, and Li2MgN2H2 in the temperature range of 180-250 ℃. From 200 to 300 ℃, the newly formed Al and Li2MgN2H2 reacted further to form Li2NH and some stable phase (AlN and Mg3N2). The H-cycling properties of the composite were further investigated by a standard Sievert's type apparatus at 150, 200 and 250 ℃,respectively. Finally, the reversibility of the newly synthesized composite was discussed.