The present study aims to consolidate information regarding the catalytic reaction mechanism of MgH2/TiO2 hydrogen storage system. Reduction of titania, resulting to evolution of a monoxide rock salt nanocrystalline phase was identified by in-situ X-ray diffraction (XRD) study of a 3 mol% TiO2 additive mixed MgH2. Existence of homogeneously distributed Ti in a crystalline rock salt matrix was confirmed by combined analysis of X - ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and elemental chemical mapping techniques. Moreover, titanium in Ti3+ and Ti2+ valance states was confirmed by X - ray photoelectron spectroscopy (XPS). Differential scanning calorimetry (DSC) study proves that the reduced Ti oxide phases promote the low temperature dehydrogenation of MgH2. The present observations reiterate that the MgO rock salt layer existing in oxide additives loaded MgH2 is not necessarily a barrier layer that blocks the diffusion of hydrogen. (C) 2017 Elsevier B.V. All rights reserved.