Transition metal phosphide based amorphous NiP/rGO hybrids have been successfully synthesized through a facile one-pot co-reduction method. The prepared NiP/rGO hybrids are characterized by powder X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM) and energy dispersive X-ray detector (EDX) techniques. Compared with Ni/rGO, the resulted Ni91P9/rGO hybrid exhibits superior catalytic activity toward hydrogen generation from hydrolysis of ammonia borane (NH3BH3), with turnover frequency (TOP) value of 13.3 min(-1). The activation energy (Ea) of Ni91P9/rGO for this reaction is calculated to be 34.7 kJ mol(-1), which is much lower than those of the other reported catalysts. This superior catalytic performance may be due to the good dispersibility of Ni-91/D-9 nanoparticles and the synergistic electronic interactions between nickel and phosphorus. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.