There is a great interest in the development of advanced hydrogen absorbing materials for hydrogen purification and storage. Palladium has strong potential to play a major role in many aspects of a hydrogen based economy, leading to promising applications, encompassing hydrogen purification, storage, and detection. Here, we report on the synthesis of novel Cd@Pd core/shell nanostructured materials for hydrogen sorption and storage. The effect of a capping agent was investigated, showing that it plays an important role in the formation of the uniform and small size of the Cd@Pd nanostructures. Our study has shown that the capacity for hydrogen sorption and storage depended strongly on the composition and structure of the formed Pd-based nanomaterials, as well as the applied electrode potential. The Cd@Pd core/shell nanostructure with an optimized composition of 1:2 exhibited the highest capacity for hydrogen storage, and a 340% increase was achieved in comparison with pure Pd nanoparticles. In addition, by using Cd as the core, the potentially negative environmental impact due to the toxicity of the Cd species was minimized. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved,