The hydrogen storage properties and catalytic mechanism of FeCl2-doped LiAlH4 were investigated in minute details. LiAlH4-2mol% FeCl2 samples start to release hydrogen at 76°C, which is 64°C lower than that of as-received LiAlH4. Isothermal desorption measurements show that the 2mol% FeCl2-doped sample releases 7.0wt% of hydrogen within 17min at 250°C. At lower temperatures of 110°C and 80°C, the sample can release 4.4wt% and 3wt% of hydrogen, respectively. The apparent activation energy of LiAlH4-2mol% FeCl2 samples for R2 is 105.02kJ/mol, which is 67kJ/mol lower than that of pure LiAlH4. The reaction between LiAlH4 and FeCl2 during ball milling was found by analyzing the X-ray diffraction results, and Fe-Al particles formed in-situ from the reaction act as the real catalyst for the dehydrogenation of LiAlH4.