In this work, dehydrogenation and rehydrogenation of three LiNH 2 /CaH 2 samples with LiNH 2 /CaH 2 molar ratio of 2/1, 3/1 and 4/1 were systematically investigated. Remarkable differences were observed in the temperature dependence of hydrogen desorption and subsequent absorption. LiNH 2 /CaH 2 in a molar ratio of 2/1 transforms to ternary imide Li 2 Ca(NH) 2 after desorbing about 4.5wt.% H 2 at 350°C. And it has a reversible hydrogen storage capacity of 2.7wt.% at 200°C. As for the LiNH 2 /CaH 2 mixture in a molar ratio of 4/1, it transforms to a new compound with a composition of Li 4 CaN 4 H 6 after being dehydrogenated at 350°C. The rehydrogenation of both LiCa(NH) 2 and Li 4 CaN 4 H 6 gives LiNH 2 , LiH and the solid solution of 2CaNH–Ca(NH 2 ) 2 .