Co-P-B catalyst thin films have been synthesized on Ni-foam and glass substrate by using electroless deposition (ED) and pulsed laser deposition (PLD) respectively. The efficiency of these catalyst films was tested by catalytic hydrolysis of NaBH(4) for H(2) generation. While the chemically produced Co-P-B film on Ni-foam shows similar activity as that of their corresponding powder, the Co-P-B film deposited by PLD exhibits much superior H(2) generation rate as compared to Co-P-B powder. We attribute this increased efficiency to the special features of the Co-P-B films which are in the form of nanoparticle-assembled films, a peculiar characteristic of PLD films for appropriate choice of the pulse laser parameters. The surface nanoparticle-configuration increases the active surface area and also favors electronic exchange mechanisms to promote hydrolysis process for H(2) gas generation. The films deposited by using laser energy density of 3 J/cm(2) show the highest activity in connection to the best configuration of the ablated nanoparticles. Different numbers of Co-P-B layers were deposited on Ni-foam by ED and it was found that at least four layers are required for complete coverage of the foam to have the best activity. (C) 2010 Elsevier B.V. All rights reserved.