The Metal-N-H system for hydrogen storage has been developed in recent years and is considered to be a promising solution. Here we report a potential compound for hydrogen storage, LiNHNH2, which is a white solid with 8.0 mass% theoretical hydrogen content and can be synthesized from anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic behaviours and hydrogen storage properties of this compound were firstly investigated and are discussed in this paper. We demonstrate the decomposition pathway of LiNHNH2 and reveal that an alkali metal hydride such as LiH can significantly increase the hydrogen desorption from LiNHNH2. Moreover, LiNHNH2 can also be used for destabilizing other hydrogen storage systems owing to its instability. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.