Amorphous Co-W-P catalysts were prepared on Cu substrates by electrodeposition, which have been investigated as the catalyst for hydrogen generation from alkaline NaBH4 solution. The surface morphology and chemical composition of the as-prepared Co-W-P catalysts were analyzed in relation to the cathodic current density and the electrodeposition time. The hydrogen generation rate for the optimized Co-W-P catalyst is measured to be 5000 mL (min g-catalyst)(-1) at 30 degrees C. From hydrogen generation tests in solutions with the various concentrations of NaBH4 and NaOH, there were optimum concentrations for both NaBH4 and NaOH, above or below which the hydrogen generation rate decreased. Furthermore, the as-prepared catalyst also showed good cycling capability and the activation energy for hydrolysis of NaBH4 by the Co-W-P catalyst was calculated to be 22.8 kJ/mol, which was lower than other reported Co-based catalysts. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.