Hydrogen is considered as the ideal candidate as an energy carrier for both mobile and stationary applications. However, the lack of efficient onboard hydrogen storage technology is becoming one of great obstacles impeding their industrial applications. Lithium borohydride (LiBH4) has been attracting a great deal of attention as a hydrogen storage material with high gravimetric hydrogen capacity. This manuscript about LiBH4 includes the synthesis, hydrolysis, structure, dynamics, intermediate compound, and the de/rehydrogenation properties improvement of LiBH4. LiBH4 can be synthesized by several methods, for example, direct synthesis from elements. In the hydrolysis of LiBH4 with the liberation of hydrogen gas, the byproduct will be different under different conditions. Structurally, LiBH4 has four different phases in experiment: Pnma, P6(3)mc, Ama2 and Fm-3m. Dynamically, the high temperature (HT) phase of LiBH4 is a lithium fast-ion conductor. In the hydrogen desorption reaction of LiBH4, Li2B12H12 among the possible intermediate compounds is studied the most. Several methods have been proposed to improve the de/rehydrogenation properties of LiBH4. The first method is "destabilization" of the LiBH4. The second one is the use of catalyst. The third one is nanoscaffolding incorporation. The de/rehydrogenation properties of LiBH4 have been changed considerably through the great efforts of researchers in recent years. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.