Low cost and catalytically effective transition metal catalysts are highly wanted in developing on-demand hydrogen generation system for practical onboard application. By using a modified electroless plating method, we have prepared a robust Co-W-B amorphous catalyst supported on Ni foam (Co- W-B/Ni foam catalyst) that is highly effective for catalyzing hydrogen generation from alkaline NaBH4 solution. It was found that the plating times, calcination temperature, NaBH4 and NaOH concentrations all exert considerable influence on the catalytic effectiveness of Co-W-B/Ni foam catalyst towards the hydrolysis reaction of NaBH4. Via optimizing these preparation and reaction conditions, a hydrogen generation rate of 15 L/min g (Co-W-B) has been achieved, which is comparable to the highest level of noble metal catalyst. In consistent with the observed pronounced catalytic activity, the activation energy of the hydrolysis reaction using Co-W-B/Ni foam catalyst was determined to be only 29 kJ/mol. Based on the phase analysis and structural characterization results, the mechanism underlying the observed dependence of catalytic effectiveness on the calcination temperature was discussed. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.