Chemical hydrogen storage, endowed with superiorities of safety and efficiency, has been regarded as one of the most promising approaches. The design and synthesis of metallic catalytic system is an key step for development of chemical hydrogen storate materials. In this paper, we report that RhNi nanocatalyst, formed by spontaneously alloying of well dispersed Rh and Ni NPs, exhibits much higher performance in the catalytic dehydrogenation of hydrous hydrazine. Copyright (C) 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.