This study proposes a p-type/n-type heterojunction system for electrochemically hydrogen storage. The electrochemical investigation was done as a simple method to evaluate storage capacity. The p-type NiO/n-type CeO2 mesoporous nanocomposites were prepared via a facile thermal decomposition way that is better than the carbohydrates as a green capping agent. For the first time, the electrochemical hydrogen storage behavior of this nanocomposite was evaluated by chronopotentiometry technique in a potassium hydroxide aqueous solution (6 M KOH) under 1 mA current. The electrochemical measurements display that the hydrogen storage capacity is largely dependent on the design of the nanostructures. Sample No. 2 with the plate-like architecture has higher hydrogen storage capacity than sample No. 1 having particle architecture. The plate-like architecture increases the storage capacity by reducing the diffusion pathway, increasing the surface area, and buffering the volume change during cycling. The hydrogen storage capacity for sample No. 1 and 2 was obtained approximate to 5500 and 6850 mAh/g, respectively. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.