In this study, we synthesized ZrO2 nanorods through a hydrothermal process as a catalyst precursor for the reversible hydrogen storage reaction between 2LiH + MgB2 and 2LiBH(4) + MgH2. The 2LiH + MgB2 composites doped with the ZrO2 nanorods demonstrated superior and stable hydriding/dehydriding kinetics upon cycling. The XRD, SEM and HRTEM results revealed that the doped ZrO2 nanorods were transformed into ZrB2 nanoparticles with a size of a few nanometers during the first hydrogenation. The initial nanosize of the ZrO2 catalyst precursor accounted for the formation of extremely fine ZrB2 nanoparticles, which acted as heterogeneous nuclei of MgB2. The present study provides a new route for performance enhancement of complex hydride composites through manipulating the nanostructure of catalysts. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.