For the first time, ultrafine Ru nanoparticles with mean diameter of 2 nm are successfully deposited on MIL-96 by using a simple liquid impregnation strategy, and tested for catalytic hydrolysis of ammonia borane. The powder X-ray diffraction, N-2 physical adsorption, transmission electron microscopy, energy-dispersive X-ray spectroscopy and inductively coupled plasma-atomic emission spectroscopy measurements are employed to characterized the Ru/MIL-96 catalysts. Thanks to the unique 3D structure of MIL-96, Ru NPs supported on MIL-96 exhibit much enhanced catalytic activity compared with other commercial supported materials and graphene, with the TOF value of 231 mol H-2 min(-1) (mol Ru)(-1), which is among the highest value ever reported. Moreover, this simple method can be extended to facile synthesis of other MOFs supported monometallic and polymetallic NPs for more application. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.