A series of Ni-Co-B catalysts were synthesized by a two-step technique, namely, chemical reduction was used to prepare the precursors, and heat-treatment was used to adjust the crystal structures. The structures of the as-prepared Ni-Co-B catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption test. The catalytic activities of the Ni-Co-B catalysts for NaBH4 hydrolysis were evaluated in a successive hydrogen generation mode, where a 5% NaBH4 + 1% NaOH solution was pumped into the hydrogen generation reactor with a feeding rate of 5 ml per minute. It is found that the heat-treatment affects the crystal structure, the apparent morphology, the oxidation state, the surface structure, as well as the hydrogen generation performances of the Ni-Co-B catalysts. The sample treated at 673 K achieves an average hydrogen generation rate of 708 ml min(-1) g(-1) (catalyst), which can give successive hydrogen supply for an 115 W portable proton-exchange membrane fuel cell (PEMFC). (C) 2011 Elsevier B.V. All rights reserved.