Electrochemical CO ₂ reduction provides a potential means for synthesizing value-added chemicals over the near equilibrium potential regime, i.e., formate production on Pd-based catalysts. However, the activity of Pd catalysts has been largely plagued by the potential-depended deactivation pathways (e.g., α -PdH to β -PdH phase transition, CO poisoning), limiting the formate production to a narrow potential window of 0 V to −0.25 V vs. reversible hydrogen electrode (RHE). Herein, we discovered that the Pd surface capped with polyvinylpyrrolidone (PVP) ligand exhibits effective resistance to the potential-depended deactivations and can catalyze formate production at a much extended potential window (beyond –0.7 V vs. RHE) with significantly improved activity (~14-times enhancement at −0.4 V vs. RHE) compared to that of the pristine Pd surface. Combined results from physical and electrochemical characterizations, kinetic analysis, and first-principle simulations suggest that the PVP capping ligand can effectively stabilize the high-valence-state Pd species (Pd ^δ+ ) resulted from the catalyst synthesis and pretreatments, and these Pd ^δ+ species are responsible for the inhibited phase transition from α -PdH to β -PdH, and the suppression of CO and H ₂ formation. The present study confers a desired catalyst design principle, introducing positive charges into Pd-based electrocatalyst to enable efficient and stable CO ₂ to formate conversion.