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Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO₂ reduction. Palladium functionalized with a chelating tris‐N‐heterocyclic carbene (NHC) ligand (Pd‐timtmb^Me) exhibits a 32‐fold increase in activity for electrochemical reduction of CO₂ to C1 products with high Faradaic efficiency (FE_C1=86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC‐ligated Pd electrode (Pd‐mimtmb^Me). The results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular‐materials interfaces enabled by surface organometallic chemistry.