The report describes the effect of TiO2 nano particles on the hydrogenation characteristics of promising Li-Mg-N-H hydrogen storage system. The effect of different particle size of TiO2 (200, 25 and 7 nm) on de/re-hydrogenation characteristics of Mg(NH2)(2)/LiH mixture has been investigated. Desorption kinetics of Li-Mg-N-H system with 25 nm TiO2 gets enhanced upto similar to 25% as compared to the pristine material kinetics at 453 K (180 degrees C). The report also deals mechanistic approach for hydrogen release from Li-Mg-N-H system in the presence of TiO2 nanoparticles through XPS analysis of catalyzed sample at various stages of reaction. The XPS analysis confirms that during dehydrogenation nitrogen atom present in Li-Mg-N-H system share their lone pair electrons to Ti (present in TiO2) and provides an alternate decomposition path which has lower activation energy for dehydrogenation. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.