A detailed analysis of the dehydrogenation mechanism and reversibility of LiBH₄ doped by active Al* derived from AlH₃ was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD), scanning electronic microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results show that the dehydrogenation of LiBH₄/Al* is a five-step reaction: (1) LiBH₄ + Al → LiH + AlB₂ + “Li-Al-B-H” + B₂H₆ + H₂; (2) the decomposition of "Li-Al-B-H" compounds liberating H₂; (3) 2LiBH₄ + Al → 2LiH + AlB₂ + 3H₂; (4) LiBH₄ → LiH + B + 3/2H₂; (5) LiH + Al → LiAl + 1/2H₂. And the reversibility of LiBH₄/Al* composite is based on equation as follows: LiH + LiAl + AlB₂ + 7/2H₂ ↔ 2LiBH₄ + 2Al. The extent of dehydrogenation reaction between LiBH₄ and Al* greatly depends on the precipitation and growth of reaction products (LiH, AlB₂ and LiAl, etc.) on the surface of Al*. A passivation shell of Al* formed by these products is the kinetic barrier to the dehydrogenation of LiBH₄/Al* composite.