In this study, the metallurgical melting Mg-10wt.%Ni (Mg10Ni) alloy is firstly modified by high-energy ball milling (HEBM) and then surface catalysts expanded graphite (EG) or MoS2 or EG-MoS2 are introduced to prepare Mg10Ni-M (M = EG, MoS2, and EG-MoS2) composites. The effects of surface catalysts on hydrolysis hydrogen generation of HEBM Mg10Ni alloy are comprehensively investigated. Their kinetics, rate-limiting steps, and apparent activation energies are investigated by fitting the hydrolysis curves at different temperatures. The results indicate that the total hydrogen generation capacities of prepared Mg10Ni-M (M = EG, MoS2, and EG-MoS2) composites are 200, 170, 674, and 720 mL center dot g(-1) within 1 minute at 291 K. The capacity and yield of Mg10Ni are 500 mL center dot g(-1) and 56% within 15 minutes. The surface catalysts EG or MoS2 or EG-MoS2 can distinctly elevate the initial H-2 produce rate and promote the complete hydrolysis process. The highest capacity and generation yield within 15 minutes are 740.8 mL center dot g(-1) and 91% obtained by HEBM Mg10Ni-EG-MoS2 composite at 291 K. The surface catalysis can promote high generation yield of Mg10Ni alloy in a short time.