Uniformly dispersed Rh (0) nanoparticles supported on zirconia nanopowder were synthesized by a two-step and simple ex-situ method summarized by mixing rhodium (III) chloride hydrate with zirconia (nano-ZrO2) aqueous solution in ambient conditions followed by reduction with NaBH4. The ex-situ prepared nano-ZrO2 supported Rh (0) nano-particles (Rh/nano-ZrO2) were characterized by various spectroscopic methods, including TEM, TEM-EDX, HR-TEM, P-XRD, XPS and ICP-OES. The catalytic activity of Rh (0) nano-particles is 1050 h(-1) in terms of initial turnover frequency (TOF), which is the first study in the literature to produce hydrogen by catalytic methanolysis of methylamine-borane. In addition, the catalytic methanolysis of methylamine-borane by using Rh (0) nanoparticles was carried out in different catalyst/substrate concentrations and different temperatures to reveal rate equation and kinetic parameters. Consequently, Rh (0) nanoparticles are taken into account as an encouraging catalyst for the methanolysis of methylamine-borane and for providing a more fertile hydrogen storage gain in fuel cell operations. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.