The ZnAl2O4 spinel was synthesized by a facile thermal decomposition method using green chemistry. For the first time, the electrochemical hydrogen storage performances and mechanisms of the ZnAl2O4 was studied by the galvanostatic charge-discharge method in 6 M KOH aqueous medium under 1 mA current. Anionic, cationic and polymeric surfactants were used to increase of hydrogen storage and specific area of ZnAl2O4 spinel. The composition, structure, morphology and specific surface area of the samples were characterized. The maximum measured discharge capacities of ZnAl2O4, ZnAl2O4/CTAB, ZnAl2O4/PVP and ZnAl2O4/SDS were 1250, 3000, 3250 and 4000 mAh/g, respectively. These samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), X-ray energy dispersive spectroscopy (EDS), N-2 adsorption (BET) and transmission electron microscope (TEM). (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.