Methanol steam reforming (MSR) and hydrolysis of metal hydrides are two important hydrogen generation reactions with complementary characteristics. Coupling of the above two reactions leads to better hydrogen generation performance. The CO2 generated from MSR can be absorbed by the hydroxide generated from hydrolysis, leading to higher H2 purity. The hydrolysis heat can be utilized to drive the endothermic MSR reaction. By carrying out MSR on a CaH2-CuO composite, a hydrogen density of 6.56 wt% based on all the reactants with H2 purity higher than 99% can be obtained at 250 °C.