Catalyst study is a central issue in the development of sodium borohydride (NaBH4)-based hydrogen generation systems. Here, we report the preparation, characterization and utilization of a novel cobalt-molybdenum-boron (Co-Mo-B) catalyst. Our study found that the Co-Mo-B catalyst prepared by chemical reduction method using an ethylene glycol solution of cobalt chloride exhibits remarkably higher catalytic activity than the Co-B and Co-Mo-B catalysts prepared in aqueous solution. On the basis of the phase, microstructure and elemental chemical state analyses, the mechanistic reasons for the improved performance of the newly prepared Co-Mo-B catalyst were discussed. Our study demonstrated that the combined usage of concentrated NaBH4 solution, Co-Mo-B catalyst and a small amount of Al powder constitutes a high-performance hydrogen generation system, which can yield >6 wt% hydrogen with fast kinetics and high fuel conversion. (C) 2012 Elsevier B.V. All rights reserved.