Abstract

The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single‐atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity‐activity dilemma. In this study, we developed a single‐atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60% with a partial current density of ‐482.7 mA cm‐2. Mechanistic investigations revealed that the incorporation of single Co atoms enhances the activation and dissociation of H2O molecules, thereby lowering the energy barrier for the hydrogenation of *CO intermediates. In situ spectroscopic experiments and density functional theory simulations further demonstrated that the modulation of the *CO adsorption configuration, with stronger bridge‐binding, favours deep reduction to CH4 over the C‐C coupling or CO desorption pathways. Our findings underscore the potential of Co1Cu catalysts in overcoming the selectivity‐activity trade‐off, paving the way for efficient and scalable CO2‐to‐CH4 conversion technologies.