In this study the amorphous Co-P alloy was electrodeposited on Cu sheet to produce a film form catalyst for hydrogen generation reactions. The effect of NaH2PO2 concentration on the microstructures of Co-P alloys and their catalytic activities for hydrolysis of NaBH4 were investigated. Experimental results showed that the deposited Co-P alloys exhibited amorphous structure and when 1.0 M NaH2PO2 was used, the highest hydrogen generation rate of 5965 mL (min g-catalyst)(-1) was achieved. This rate was 1.4 folds higher than the reported electroless-deposited Co-P catalysts. Furthermore, the activation energy for hydrolysis of NaBH4 was as low as 23.9 kJ mol(-1). The durability of the Co-P catalyst was also tested and showed stable activity in 5 cycles. (c) 2013 Elsevier B.V. All rights reserved.