The synergistic effect of 3D carbon support on Pd-based catalyst and its performance toward direct alcohol oxidation reaction is reported here. The surface of 3DrGO-MWCNTs support was modified by loading different amounts (5-20 wt%) of cerium oxide (CeO2) by wet impregnation method. Further, Pd nanoparticles were dispersed over CeO2/3DrGO-MWCNTs nanocomposites by chemical reduction method. The synthesized nanocomposites were characterized by various techniques such as XRD, XRF, SEM, TEM, Raman, and XPS analysis. The electro-oxidation performance and long-term stability of the Pd/CeO2/3DrGO-MWCNTs electro-catalyst were measured by CV, LSV, and CA analysis. The modification of the catalysts surface by cerium oxide Pd/10CeO(2)/3DrGO-MWCNTs leads to a higher anodic peak current of about138.43 mA/cm(2) and 91.72 mA/cm(2) when compared to the Pd/3DrGO-MWCNTs and Pd/C for ethanol and methanol electro-oxidation. In addition, the catalyst showed the highest electro chemical active surface area. The present work demonstrates a possible way to fabricate a nanostructure catalyst to improve the performance of electro-catalytic reactions. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.