Systematic studies of Co-Mo-B-P alloy catalysts, synthesized by chemical reduction methods, were conducted for H 2 generation by hydrolysis of ammonia borane (AB). The molar concentrations of Mo and P were optimized in the alloy to obtain the best catalytic activity. The combined promoting effects induced by Mo and P in the quaternary alloy caused the H 2 generation rate to increase by ̃7.5 times as compared to the undoped-Co-B catalyst. XPS, XRD, SEM, and BET surface area analyses were carried out to understand the promoting role of each dopant element during AB hydrolysis. In the Co-Mo-B-P alloy catalyst, Mo in form of oxides acts as an atomic barrier to avoid Co-B particles agglomeration to preserve the effective surface area. These oxidized species also act as Lewis acid sites to enhance the absorption of reactant to further assist the hydrolysis reaction over alloy catalysts. The role of P in the alloy catalyst is to create a higher number of Co active sites on the catalyst surface as confirmed by XPS. These combined promoting effects provided by P and Mo doping in the Co-B catalyst reduce the activation energy to the lowest value (23 kJ/mol) in the hydrolysis of AB.