A systematic and comparative study is conducted on Co-B-based ternary alloy catalysts for H-2 generation by hydrolysis of NaBH4. Various transition metals, namely Ni, Fe, Cu, Cr, Mo, and W, were added to Co-B catalyst by chemical reduction of the corresponding metal salts. All the transition metals in the Co-B compounds behave in a dissimilar manner while influencing the catalytic activity. Cr, W, Mo, and Cu impose significant promoting effects on the Co-B catalyst by increasing the H-2 generation rate by 3-4 times when compared to the undoped catalyst. On the contrary, Ni and Fe are only able to create a marginal increment in the catalytic performance of the Co-B catalyst. The metal/(Co + metal) molar ratio was varied in the catalyst in order to study the effect of metal doping on surface morphology, electronic interaction, and catalytic efficiency of the alloy catalyst. This systematic variation also contributed to clarify the role of each dopant metal in the electron exchange mechanism involved in NaBH4 hydrolysis. The promoting effects of the dopant metals are mainly discussed in terms of large active surface area, ability to act as Lewis acid sites for better absorption of OH- group, electronic interaction with Co active metal, and amorphous nature of the alloy catalyst. (C) 2010 Elsevier Inc. All rights reserved.