[Display omitted] • Pd/CeO 2 exhibits higher catalytic activity than Pd/OCNT for glucose oxidation. • The catalyst deactivation is suppressed on Pd/CeO 2 due to their strong interaction. • The adsorption of gluconic acid is weakened on Pd/CeO 2. • The OH ads generated on the CeO 2 surface accelerates the oxidation of glucose. • Increasing the oxygen vacancy of CeO 2 results in the enhanced catalytic activity. Catalytic oxidizing of glucose into gluconic acid (GLUC) provides an attractive and feasible pathway for the high value-added utilization of glucose, in which Pd-based catalysts deliver outstanding catalytic performance. However, the surface poisoning of Pd caused by the strong adsorption of GLUC becomes the bottleneck for their further applications. Herein, oxygen-vacancy-riched ceria supported Pd catalyst (Pd/CeO 2) is employed, which effectively alleviates the catalyst deactivation, and realizes high catalytic activity and stability with 100 % GLUC selectivity for glucose oxidation at room temperature. Kinetic analysis confirms the strong anti-poisoning ability of Pd/CeO 2. The superior catalytic performance is attributed to the modulation of the electronic structure of Pd nanoparticles by the strong metal-support interaction between Pd and CeO 2. The valence band photoemission spectra reveal that the downshift of the d-band center of Pd leads to the weak adsorption of GLUC on Pd/CeO 2. Meanwhile, kinetic isotope effect experiments indicate that the OH ads generated from H 2 O dissociation on the CeO 2 surface affords another path for glucose oxidation, thus improves the catalytic activity. [ABSTRACT FROM AUTHOR]