Developing non-precious metal catalysts with high activity is crucial for the extensive applications of the proton exchange membrane fuel cell (PEMFC). Herein, we have prepared cobalt-copper-boron (Co-Cu-B) nanoparticles by a modified chemical reduction route where Ni foam was used as an initiation medium for the efficient hydrolysis of alkaline sodium borohydride (NaBH4) solution. The influence of the synthetic condition (such as Cu2+ concentration, pH value and the concentration of reducing agent) on the catalytic activities has been explored. The catalytic hydrolytic tests reveal that the as-obtained Co -Cu-B nanoparticles with hollow spherical structure shows highly efficient catalytic activity, affording a hydrogen generation rate (HGR) of 3554.2 mL(H2).g(catal)(-1). min(-1) under room temperature, and a lower activation energy of 52.0 kJ mol(-1), which overtakes the activities of previous reported most non-precious metal catalysts, even some precious catalysts. The kinetics results show that the catalytic hydrolysis process of alkaline NaBH4 solution is a zero-order reaction in view of the amount of Co-Cu-B catalyst, meaning that the reaction rate is independent of the catalyst amount. This study offers us a promising non-precious metal catalyst toward dehydrogenation from the hydrolysis of NaBH4 to further speed up the application steps. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.