LiNH(BH3)NH2BH3, the first example of metal-substituted hydrazine bisborane (HBB), is synthesized via the reaction between HBB and n-butyllithium in ether solution. B-11 NW. and Fourier transform infrared spectroscopy indicate a new structure, in which one of the N-H bonds is replaced by a N-Li bond. The X-ray diffraction pattern of the product also indicates the formation of a new crystal structure. This compound releases hydrogen at 126 and 170 degrees C with satisfactory purity and exhibits superior hydrogen storage properties compared with HBB. Differential scanning calorimetry measurement suggests the dehydrogenation reaction of this compound is less exothermic than that of HBB.