The as-cast magnesium-nickel-cerium (Mg-Ni-Ce) alloys with nominal component (Mg-10 wt% Ni)(1-x)Ce-x (x = 0, 5, 10, 15 wt%) are optimized by high-energy ball milling (HEBM). Expandable graphite (EG) and molybdenum disulfide (MoS2) have been introduced as surface catalysis to form (Mg10Ni)(95)Ce-5-5 wt% EG-5 wt% MoS2 composite. The synergetic effects of HEBM and catalysts on H-2 production of (Mg10Ni)(95)Ce-5 are comprehensively studied. The thermodynamics are studied by H2 generation curves fitting. The HEBM 0Ce, 5Ce, 10Ce and 15Ce alloys at 291 K can generate 530, 747, 720 and 487 mL g(-1) H-2 with conversion yields of 59%, 87%, 89% and 64% in initial 15 min, respectively. The addition of surface catalysts EG-MoS2 can further enhance the initial hydrogen generation rate and the final conversion yield within short period at room temperature. 773 mL g(-1) H-2 corresponding to 95% conversion yield can be obtained by HEBM (Mg10Ni)(95)Ce-5-EG-MoS2 within 1 min at 291 K. The synergetic effects of HEBM and EG-MoS2 can promote rapid initial generation rate and high conversion yield of hydrolysis hydrogen generation of (Mg10Ni)(95)Ce-5-EG-MoS2 composite. This work indicates a promising way to synthesize Mg-based alloys with rapid initial hydrolysis H-2 generation kinetics and high conversion yield within a short period.