The catalytic effects of Co@C additive on hydrogen storage properties of LiAlH4 prepared by ball milling have been systematically investigated. The onset desorption temperature of Co@C–LiAlH4 sample is 100.0°C, which is 51°C lower than that of as-received LiAlH4. Isothermal desorption results show that for Co@C–LiAlH4 dehydrogenated at 130°C, 4.58wt% of hydrogen can be released with 180min, which is 3.56wt% higher than that of as-received LiAlH4 under the same conditions. Approximately 7.05wt% of hydrogen is released at 150°C. Through the Kissinger desorption kinetics analyses, the apparent activation energy, Ea, of Co@C–LiAlH4 is calculated as 95.36kJmol−1 H2 and 115.6kJmol−1 H2 for the first two decomposition processes, respectively. It indicates that dehydrogenation kinetics of LiAlH4 matrix considerably improves by doping the Co@C catalyst.