In the present study, nanostructured Ni-B catalysts were successfully prepared in ethanol medium using the chemical reduction method for hydrogen production from the catalytic hydrolysis of sodium borohydride (NaBH4). Ni-B nanostructures were characterized by several analysis methods including XRD, SEM/EDS, FT-IR and BET. The effects of factors such as solution temperature, NaBH4 loadings, catalyst amount and NaOH concentration on the performance of these catalysts in the production of hydrogen from alkaline NaBH4 solutions were investigated in detail. In addition, the Ni-B catalyst prepared in ethanol medium and subjected to plasma for the hydrogen production from the catalytic hydrolysis of NaBH4 was investigated. The Ni-B catalyst prepared in ethanol medium showed maximum hydrogen production rate (1000 mL min(?1)gcatalyst(?1)) which was approximately 2 times higher than the rate obtained from the Ni-B catalyst prepared in water (400 mL min(?1)gcatalyst(?1)) and acethone (550 mL min(?1)gcatalyst(?1)). The Ni-B nanoparticles showed the best catalytic activity at 333?K with a maximum hydrogen production rate of 7134 mL min(?1)gcatalyst(?1) and activation energy of 46.83?kJmol(?1) for the NaBH4 hydrolysis reaction in the Ni-B catalysts prepared in ethanol and subjected to plasma. As the Ni-B catalyst is inexpensive and easy to prepare, it is feasible to use this catalyst in the construction of practical fuel cells for portable and in situ applications.