<p>The analysis presented in this manuscript helps bridge an important fundamental discrepancy between the existing theoretical and experimental knowledge regarding the performance of Ag catalysts for CO<sub>2</sub> electrochemical reduction (CO<sub>2</sub>ER). The results demonstrate how the intermediate species *OCHO is formed readily en-route the HCOO<sup>– </sup>pathway and plays a decisive role in determining selectivity of a predominantly CO producing catalyst such as Ag. Our theoretical and experimental approach develops a better understanding of the nature of competition as well as the complex interactions between the reaction intermediates leading to CO, HCOO<sup>–</sup> and H<sub>2</sub> during CO<sub>2</sub>ER.</p><p><br></p><p>Details of computational and experimental methods are present in the Supporting Information provided. </p><p><br></p><p><br></p>
