An Li-Mg-N-H system has been synthesized from Mg(NH2)2 and LiH in the ratio 3:8 by a ball-milling process and its dehydrogenation/rehydrogenation properties at around 190°C were investigated. XRD, FTIR and TG results showed that the system was composed of an LiH phase and an amorphous Mg(NH2)2 phase with a purity of 90%. A reversible hydrogen storage capacity of 4.7% was observed during the first cycle and more than 90% of the stored hydrogen was desorbed within 100 min for each cycle. However, only 4.2% and 2.9%, respectively, of hydrogen was observed during two subsequent dehydrogenation cycles. In situ GC results showed that no NH3 could be observed during the dehydrogenation process. On the basis of the SEM and XRD results, the loss in hydrogen storage capacity can be mainly attributed to agglomeration, oxidation and crystallization of the materials.