The nanostructured Ni-B catalysts were synthesized on the Cu sheet by electroless plating at ambient temperature. The catalytic performance for hydrogen generation from hydrolysis of sodium borohydride solution has been investigated. The concentration of the reducing agent was shown to have a significant influence on the hydrogen generation performance. The Ni-B catalyst deposited with 0.08 g L-1 reducing agent showed excellent catalytic activity due to the smaller particle or crystal size and the higher surface roughness. The highest hydrogen generation rate could reach 4991.8 mL min(-1) g(-1) and the lower activation energy was 36.3 kJ mol(-1). The Ni-B catalyst also displayed high stability. The catalytic activity could retain about 80.5% of its initial value after 5 cycles. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.