In this paper, the novel Cu@CoNi tri-metallic core-shell NPs have been synthesized by a facile and efficient in situ method at room temperature. It exhibits superior catalytic activity towards the hydrolysis dehydrogenation of ammonia borane (NH3BH3, AB). In these series nanoparticles, the [email protected] core-shell NPs showed the best catalytic performance that the maximum hydrogen generation rate is 7340.80 mL min(-1)g(-1) at 298 K. The hydrolysis reaction towards AB was proved to the first order by the [email protected] NPs via kinetic studies. The activation energy was 36.08 kJ mol(-1). Even after five recycle experiment, the catalysts also showed a good recycle stability in aqueous solution owing to the synergistic effect of Cu, Co and Ni in the tri-metallic core-shell NPs. The core-shell NPs/carbon composites also showed the better catalytic performance for hydrolysis to ammonia borane and rGO is proved to be the best support to catalyst. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.