We report the preparation of Ni3B and carbon-supported Ni3B (denoted as Ni3B/C) nanoparticles, and their catalytic performance for hydrogen generation from hydrolytic dehydrogenation of ammonia borane (NH3BH3, AB). Ni3B and Ni3B/C were prepared via a chemical reduction and crystallization in tetraethylene glycol solution. The obtained Ni3B catalysts are in well-defined crystalline state and Ni3B/C catalysts have a high dispersion in the carbon. The hydrogen generation measurement shows that the carbon-supported Ni3B presents enhanced catalyst activity during hydrolytic dehydrogenation of AB. Among the as-prepared Ni3B/C catalysts, Ni3B/C with 34.25 wt% Ni3B loading displays the best catalytic activity, delivering a high hydrogen release rate of 1168 mL min(-1) g(-1) and the lower activation energy of 46.27 kJ mol(-1). The kinetic results show that the hydrolysis is a first-order reaction in catalyst concentration, while it is a zero-order in AB concentration. Furthermore, the Ni3B/C is a recyclable catalyst under mild reaction conditions, indicating that the carbon-supported Ni3B is a promising catalyst for AB hydrolytic dehydrogenation. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.