In this paper, a new synthetic strategy towards functionalized ZnO-HMD@ZnO-Fe/Cu core-shell using solgel process modified by chemical grafting of hexamethylenediamine (HMD) on the core and in-situ dispersion of Cu/Fe as metallic nanoparticles (M-NPs) on the shell. The as-prepared core-shell materials were fully characterized by transmission electron microscopy, X-ray powder diffractometry, diffuse reflectance and FT-IR spectrophotometery, photoluminescence, and complexes impedance spectroscopy measurements. The XRD patterns agreed with that of the ZnO typical wurtzite structure, indicating good crystallinity of ZnO-HMD@ZnO-Fe/Cu, with the presence of Fe-0 and Cu-0 phases. Hexamethylenediamine grafting and M-NPs insertion were highly activated and enhanced the core and shell interface by the physiochemical interaction. After functionalization, luminescence intensities and electrical properties of both core and core-shell nanoparticles are improved, indicating the effects of the surface groups on the charge transfer of ZnO-HMD@ZnO-Fe/Cu. The hydrogen capacity retention was depended strongly on the composition and structure of the obtained core-shell. Iron/Copper-loaded ZnO-HMD@ZnO materials exhibited the highest capacity for hydrogen storage. The excellent stability and performance of the ZnO-HMD@ZnO-Fe/Cu core-shell make it an efficient candidate for hydrogen storage. (C) 2016 Elsevier Inc. All rights reserved.