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Abstract: Cr-modified Co–B (Co–Cr–B) catalyst alloy powders have been synthesized by chemical reduction of cobalt and chromium salt at room temperature to study the hydrogen production by catalytic hydrolysis of NaBH4. The Cr/Co molar ratio was varied in the catalyst in order to study the effect of Cr doping on surface modification and catalytic efficiency of Co–B catalyst. The resulting catalyst powders were characterized by scanning electron microscopy, X-ray diffraction, X-photoelectron spectroscopy, and BET surface area measurement. When the molar ratio χ Cr =Cr/(Cr+Co) exceeds 9% the BET surface area of the Co–Cr–B catalyst increases by one order of magnitude as compared to that of Co–B catalyst. The catalytic activity of the Co–Cr–B for hydrogen production depends on Cr concentration: specifically, the activity increases by increasing χ Cr up to about 4% and then it gradually decreases by further increasing χ Cr. We established that the increased catalytic activity is related to the formation of chromium oxide on the catalyst surface, with the oxide favoring the dispersion of Co–B particles resulting in high catalyst surface area. However as χ Cr exceeds 4%, Cr starts to cover the Co active sites and the corresponding catalytic activity decreases. The highest catalytic activity was obtained at the optimum Cr-content, χ Cr =4%, in Co–Cr–B catalyst, showing nearly 4 times higher H2 generation rate than that of pure Co–B catalyst. Kinetic studies on the hydrolysis reaction of NaBH4 with Co–Cr–B catalyst reveal that the concentrations of both NaBH4 and NaOH have essentially no effects on hydrogen generation rate. The promoting effect of Cr in Co–Cr–B catalyst results in lower activation energy for hydrogen production, which is 37kJmol−1 as compared to 45kJmol−1 obtained with pure Co–B powder. Finally, the possible role of Cr3+ species in the electron exchange mechanisms involved in NaBH4 hydrolysis with the Co–Cr–B catalyst has been discussed. [Copyright &y& Elsevier]