Herein, we report the preparation and characterization of rhodium(0) nanoparticles supported on hydroxyapatite (Ca-10(OH)(2)(PO4)(6), HAP) and their catalytic use in the hydrolysis of hydrazine-borane, which attracts recent attention as promising hydrogen storage materials. Hydroxyapatite supported rhodium(0) nanoparticles were readily prepared by the hydrazine-borane reduction of rhodium(III)-exchanged hydroxyapatite in situ during the hydrolysis of hydrazine-borane at room temperature. Characterization of the resulting material by ICP-OES, TEM, SEM, EDX, XRD, XPS spectroscopies and N-2 adsorption-desorption technique, which shows the formation of rhodium(0) nanoparticles well dispersed on hydroxyapatite support. The catalytic performance of these new supported rhodium(0) nanopaiticles in terms of activity, lifetime and reusability was tested in the hydrolysis of hydrazine-borane. They were found to be highly active, long-lived and reusable catalyst in this important catalytic reaction even at low temperatures and high initial [substrate]/[catalyst] conditions. This report also includes the detailed kinetic study of the hydrolysis of hydrazine-borane catalyzed by hydroxyapatite supported rhodium(0) nanoparticles depending on the catalyst concentration, substrate concentration, and temperature. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.