Various Mg/Nb/O mixed phases have been prepared by solid state reaction in order to mimic similar compounds formed in the ball milled system composed of MgH2 and Nb2O5. The latter oxide has a role as a promoter of the hydrogen uptake and desorption in the Mg/MgH2 system for hydrogen storage. One mixed phase in particular (Mg3Nb6O11) have shown a reversible uptake of molecular hydrogen, confirmed by thermal desorption experiments followed by mass spectroscopy. Comparison of the behaviour of this phase with NbO shows, how a reversible interaction with hydrogen may be linked to the presence of octahedral niobium clusters in both oxides. (c) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.