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 catalyst's surface by cerium oxide Pd/10CeO₂/3DrGO-MWCNTs leads to a higher anodic peak current of about138.43 mA/cm² and 91.72 mA/cm² 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.