An electrodeposition method for preparing the Pd catalyst layer on graphite rod electrodes for direct formic acid oxidation is proposed in this study. This method consists of a repeated procedure involving the electrodeposition of Pd catalyst onto the graphite rods, followed by Nation coating (RENC). The structural features and electrocatalytic properties of the electrode were extensively investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results show that coating the electrode with Nation during each electrodepositing step plays a crucial role on the morphology, particle size and crystallinity of the electrocatalysts. Although the commercial Pd catalyst has the smaller particle size and more uniform distribution than that prepared by RENC, the RENC electrode exhibits almost the same electrochemical surface area, a better performance and durability toward formic acid electro-oxidation. These results can be attributed to the improved catalyst utilization resulting from the multi-layer structure and the predominance of the highly active Pd (111) crystallite phase on the surface of the catalyst layer. (C) 2012 Elsevier B.V. All rights reserved.