The effect of mesoporous Co3O4, NiCo2O4 and NiO on the hydrogen sorption performance of MgH2 was investigated. These oxides were synthesized by multi-step nanocasting and introduced during the high-energy ball milling of MgH2 powder to act as catalysts. Hydrogen desorption on the as-milled powders was assessed upon heating the samples from room temperature to 400 degrees C. In all cases, the onset temperature for desorption was lowered by taking advantage of the introduced additives. The NiO-doped sample displayed the best response, the desorption rate being 7 times faster than in pure MgH2. Complementary kinetic studies on this particular sample revealed that the sorption activation energies were much lower (50 kJ/mol for absorption and 335 kJ/mol for desorption) than the corresponding ones for undoped MgH2 (57 kJ/mol for absorption and 345 kJ/mol for desorption), thus proving the catalytic activity of the mesoporous NiO oxide. Significantly, the X-ray powder diffraction (XRPD) patterns taken on the NiO-doped sample after discharging/charging cycles revealed that Mg could fully hydrogenate at the end of the charging process, while Mg metal was still detected in the undoped (pure) sample. Favored conditions for dissociative chemisorption of hydrogen could be ascribed to the formation of metallic Ni arising from complete or partial reduction of NiO, as observed in the XRPD patterns. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.