Hydriding combustion synthesis (HCS) and mechanical milling (MM) are both well-known methods for production of magnesium-based hydrogen storage alloys. The former can produce high active hydride by a simple process, and the latter can synthesis various metastable hydrogen storage materials such as nanocrystalline, amorphous and extended solid solutions phases with excellent hydrogen sorption properties. In the present study, HCS and MM were combined, aiming to decrease sorption temperature for Mg2Ni. The high active Mg2NiH4, synthesized by HCS, was mechanically milled for 0.5, 6, 40 and 80 h with 5 wt% of graphite under argon atmosphere. The effect of the milling process on the morphology and crystal structural Of Mg2NiH4 were investigated by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The hydrogen storage properties were examined by a Sieverts type apparatus. The nanocrystalline Mg2NiH4 milled for 40h has the best sorption kinetics, which can absorb 2.4 wt% hydrogen at 303 K within 100 s in the first cycle. Several reasons are considered to explain the improvement in hydriding kinetics. (C) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.