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Metal-support interaction enhancement is critical in the fuel cell catalyst design and fabrication. Herein, taking the Pd@CeO2 system as an example, we revealed the substrate morphology coupling effect and the thermal annealing-induced Pd-O-Ce linkage enhancement in the improved catalytic capability for formic acid electrooxidation. Three well-defined CeO2 nanocrystals were employed to support Pd nanoparticles, and the best catalytic performance for formic acid oxidation and anti-CO poisoning ability was found on CeO2 plates because of