Here, first-time synthesis and characterization of highly effective and relatively low-cost poly (N-vinyl-2-pyrrolidone)-stabilized cobalt-rhodium nanoclusters and their employment as catalysts to generate hydrogen from ammonia borane via hydrolysis pathway is reported. They are readily synthesized by co-reduction of cobalt and rhodium cations in ethanol/water mixture under reflux temperature. They are found to be highly stable for a long time without any precipitation. Their size, morphology, and chemical composition are determined by advanced analytical techniques of ultraviolet-visible (UV-Vis) electronic absorption spectroscopy, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). They are found to be highly recyclable and effective catalysts for hydrogen release from ammonia borane hydrolysis reaction at very low concentrations and temperature, providing initial turnover frequency (TOF) of 154 min(-1) and activation energy of 42.7 kJ mol(-1). (C) 2020 Elsevier Ltd. All rights reserved.