NiCo nanoalloy (4-6 nm) encapsulated in grapheme layers (NiCo@G) has been prepared by thermolysis of a 3D bimetallic complex CoCo[Ni(EDTA)]2·4H2O and successfully employed as a catalyst to improve the dehydrogenation performances of LiAlH4 by solid ball-milling. NiCo@G presents a superior catalytic effect on the dehydrogenation of LiAlH4. For LiAlH4 doped with 1 wt% NiCo@G (LiAlH4-1 wt% NiCo@G), the onset dehydrogenation temperature of LiAlH4 is as low as 43 °C, which is 109 °C lower than that of pristine LiAlH4. 7.3 wt% of hydrogen can be released from LiAlH4-1 wt% NiCo@G at 150 °C within 60 min. The activation energies of LiAlH4 dehydrogenation are extremely reduced by 1 wt% NiCo@G doping.