Cobalt boride precursors were synthesized via chemical reaction of aqueous sodium borohydride with cobalt chloride, and followed by heat-treating at various temperatures. The as-prepared Co–B catalysts were characterized and analyzed by X-ray diffraction (XRD), nitrogen adsorption–desorption and catalytic activity test; and were adopted to help accelerating hydrolysis reaction of NaBH 4 alkaline solution. The Co–B catalyst treated at 500 °C exhibits the best catalytic activity, and achieves an average H 2 generation rate of 2970 ml/min/g, which may give a successive H 2 supply for a 481 W proton exchange membrane fuel cell (PEMFC) at 100% H 2 utilization.