Direct　ethanol　fuel　cells　(DEFCs)　have　been　extensively　studied　as　promising　energy　conversion　devices　due　their　non-toxicity,　low　corrosivity,　and　high　energy　and　power　densities.　However,　developing　highly　active　durable　catalysts　for　the　ethanol　oxidation　reaction　(EOR)　at　the　anode　remains　a　significant　challenge.　Herein,　we　modulate　the　intermediate　affinity　on　Pt　nanoparticles　(NPs)　to　achieve　highly　efficient　EOR　performance　through　precise　optimization　of　the　Pt-CeO2　interface.　The　well-defined　and　fully　exposed　Pt-CeO2　interface　engineered　through　controlled　incorporation　of　CeO2　nanoclusters　within　the　hierarchical　pore　structure　nitrogen-doped　porous　carbon　(NPC).　The　high　electrical　conductivity　and　abundant　pore　structure　of　NPC　only　accelerate　the　charge　transfer　rate　but　also　enhance　the　stability　of　CeO2　through　confinement　effects.　Importantly,　experimental　and　theoretical　analyses　reveal　that　the　interaction　between　CeO2　and　Pt　strengthens　the　stability　of　Pt　NPs,　modulates　the　surface　charge　distribution　of　Pt,　and　provides　additional　adsorbed　hydroxyl　species　(OHads),　further　boosting　the　ethanol　oxidation　capability　of　Pt.　The　Pt/CeO2@NPC-300　catalyst　not　only　delivers　a　maximum　mass　activity　of　1207　mA　mgPt-1　and　retains　64.7　%　of　its　initial　performance　after　500　cycles,　but　also　exhibits　excellent　CO　tolerance.　This　study　proposes　an　innovative　catalyst　structural　design　strategy　to　advance　the　development　of　DEFCs　and　other　sustainable　energy　technologies.