In this paper, we report on the preparation, characterization and catalytic NaBH4 hydrolysis of nanostructured Co-P catalysts prepared using electroless plating method on the Cu sheet. Co-P catalysts composed of nanoplatelets, nanospheres and nanoflowers are successfully obtained by tuning the NaH2PO2 concentration. The as-prepared Co-P sample with hierarchical flower-like shape shows significantly enhanced catalytic activity during hydrolytic dehydrogenation of NaBH4, affording hydrogen release rate of 1647.9 mL min(-1) g(-1) at 30 degrees C and an activation energy of 47.0 kJ mol(-1). This enhanced activity is due to their novel nanoflower architectures made up of nanoplatelets or the high surface roughness, providing many defects of angle, step, or edge and so on, to form more active sites on the catalyst surface. Furthermore, the hydrogen generation rate decreases gradually after 11 cycles, about 61% of the initial hydrogen generation rate. The study reveals the reason may be the decrease in the amount of P that provides active metallic Co sites on the catalyst surface. (C) 2015 Elsevier B.V. All rights reserved.