We report the synthesis by ‘chimie douce’ route of high surface area (200 m2/g) nano crystalline Nb2O5 (so called p-Nb2O5) and the importance of its addition to enhance the hydrogen sorption properties of MgH2. All of the prepared Nb2O5 catalysts induce faster kinetics, up to twice the desorption rate, than commonly used commercial Nb2O5. Among them, both p-Nb2O5 and Nb2O5:350 (p-Nb2O5 heated to 350 °C) exhibit the best catalytic activity, since a 5.2 wt% hydrogen desorption was achieved at 300 °C for (MgH2)p−Nb2O5, as compared to less than 4 wt.% for commercial Nb2O5 added MgH2, (MgH2)c−Nb2O5, within 12 min. Furthermore, due to the addition of high surface area Nb2O5, the desorption temperature was successfully lowered down to 200 °C, with a significant amount of desorbed hydrogen (4.5 wt%). In contrast at this “low” temperature, (MgH2)c−Nb2O5 shows no desorption.