The hydrogen sorption behavior of the Mg2FeH6- MgH2 hydride system is investigated via in-situ synchrotron and laboratory powder X-ray diffraction (SR-PXD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), particle size distribution (PSD) and volumetric techniques. The Mg2FeH6-MgH2 hydride system is obtained by mechanical milling in argon atmosphere followed by sintering at high temperature and hydrogen pressure. In-situ SR-PXD results show that upon hydriding MgH2 is a precursor for Mg2FeH 6 formation and remained as hydrided phase in the obtained material. Diffusion constraints preclude the further formation of Mg2FeH 6. Upon dehydriding, our results suggest that MgH2 and Mg2FeH6 decompose independently in a narrow temperature range between 275 and 300 C. Moreover, the decomposition behavior of both hydrides in the Mg2FeH6-MgH2 hydride mixture is influenced by each other via dual synergetic-destabilizing effects. The final hydriding/dehydriding products and therefore the kinetic behavior of the Mg 2FeH6-MgH2 hydride system exhibits a strong dependence on the temperature and pressure conditions. © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.