Pd-CeO2/C electrocatalyst was successfully prepared by first depositing CeO2 onto carbon black through the microwave-assisted heating process under the presence of ammonium, followed by the reduction of Pd nanoparticles. In order to demonstrate the promotive role of CeO2 in the Pd-CeO2/C system, various electrochemical characterization methods were performed for the formic acid electro-oxidation. It was found that Pd-CeO2/C showed more enhanced electrocatalytic activity and improved kinetics than conventional Pd/C. It was proposed that the existence of CeO2 may promote the proceeding of the direct oxidation pathway (dehydrogenation) instead of the dehydration pathway.