Co-W-P alloy catalysts were prepared on gamma-Al2O3 supports by electroless deposition. Inductively coupled plasma atomic emission spectrometer(ICP-AES), field emission scanning electron microscope(SEM), energy dispersive X-ray spectrometer(EDS), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and nitrogen adsorption-desorption isotherm were used to characterize the Co-W-P/-gamma-Al2O3 catalysts. Hydrolysis of sodium borohydride solution to produce hydrogen was used as a probe reaction to evaluate the catalytic activity of the obtained catalysts. The influences of catalyst preparation conditions such as CoSO4/Na2WO4 concentration ratio in electroless bath, electroless deposition time and hydrolysis reaction conditions such as NaOH and NaBR4 concentrations, the amount of catalysts used and reaction temperature on the hydrogen generation rate were investigated in the paper. The results show that the obtained Co-W-P/gamma-Al2O3 catalysts exhibit excellent catalytic activity, the highest hydrogen generation rate can reach a 11.82 L min(-1) g(catalyst)(-1). The Co-W-P/gamma-Al2O3 catalysts also exhibit favorable cycling performance and lower activation energy (49.58 kJ mol(-1)). Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.