The work aims to study optimum conditions of generating hydrogen by catalyzing alkaline NaBH4 solution by optimizing formula of Co-Ni-Cr-P alloy catalysts. The Co-Ni-Cr-P alloy was coated on the surface of aluminium sesquioxide (γ-Al2O3) in the method of electroless deposition. Structure and microstructure of the Co-Ni-Cr-P/γ-Al2O3 catalysts were characterized systematically with X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM), X-ray energy dispersive spectrometer (EDS), nitrogen adsorption-desorption isotherm (BET) and inductively coupled plasma atomic emission spectrometer (ICP). Co-Ni-Cr-P alloy coating was well distributed onto the surface of carrier γ-Al2O3. According to ICP results, relative composition was 48.46wt% Co, 19.77wt% Ni, 21.02wt% Cr and 10.75wt% P (mass fraction, similarly hereinafter). Experiment parameters of electrolessly plating Co-Ni-Cr-P were: 21.96 g/L cobalt sulfate heptahydrate, 2.44 g/L nickel sulfate hexahydrate, 0.6 g/L Chromic nitrate nonahydrate, 20 g/L sodium citrate dehydrate, 10 g/L ammonium fluoride, 40 g/L sodium hypophosphite Monohydrate, pH=9 and temperature (90±1) ℃. Average hydrogen generation rate of 20 mL 4% NaBH4 solution was 1500 mL/(g?min). Reaction activation energy of the Co-Ni-Cr-P/γ-Al2O3 alloy catalysts in hydrogen generation was measured to be 45.96 kJ/mol.