For the first time, a series of highly efficient RhNiP@MOF-74 nanocomposite catalysts were synthesized by a one-step reduction process, subsequently characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). Synergistic electronic effects between Rh, Ni, and P, along with electron transfer phenomena between RhNiP and MOF-74 resulted in outstanding catalytic activities towards the dehydrogenation of hydrous hydrazine in an alkaline solution (2 M NaOH) at 50 degrees C. The turnover frequency (TOF) value of Rh47Ni18P35@MOF-74 reached 715.4 mol H-2.h(-1)(mol metal)(-1) with 100% hydrogen selectivity, and there was no significant decrease even after five cycles. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.