The Mg-10wt%Ni master alloy was firstly prepared using an electric resistance furnace under the protection of the cover reagent. Nanocrystalline alloys were obtained by spinning the molten alloy on a rotating copper wheel at a linear velocity of 35 m/s. Subsequently, the nanocrystalline alloy was high-energy ball milled (HEBM) with MWCNTs or TiF3 or both. The catalytic effect of MWCNTs or TiF3 and the synergetic catalytic effects on hydrogenation properties of Mg-based alloys were investigated. The alloys were characterized by X-ray diffraction (XRD), transition electron microscope (TEM), scanning electron microscope (SEM) equipped with an electron energy dispersion spectrum (EDS) to evaluate phase compositions, crystal structure, grain size, particle morphology and the distribution of catalyst element. Hydrogen storage capacities and the hydriding kinetics of the materials were measured using a Sievert's apparatus. Hydrogenation properties of the samples with and without catalysts were compared to understand the catalytic effect of MWCNTs and TiF3 on the hydrogenation performance of Mg-based alloys. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.