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Electrocatalysis, whose reaction venue locates at the catalyst–electrolyte interface, is controlled by the electron transfer across the electric double layer, envisaging a mechanistic link between the electron transfer rate and the electric double layer structure. A fine example is in the CO₂ reduction reaction, of which rate shows a strong dependence on the alkali metal cation (M⁺) identity, but there is yet to be a unified molecular picture for that. Using quantum-mechanics-based atom-scale simulation, we herein scrutinize the M⁺-coupling capability to possible intermediates, and establish H⁺- and M⁺-associated ET mechanisms for CH₄ and CO/C₂H₄ formations, respectively. These theoretical scenarios are successfully underpinned by Nernstian shifts of polarization curves with the H⁺ or M⁺ concentrations and the first-order kinetics of CO/C₂H₄ formation on the electrode surface charge density. Our finding further …