We have devised two groups of Cu-based electrocatalysts through two approaches: surface modification with Ag single-atoms and co-catalysis between Cu and Nitrogen Doped Carbon (NDC). These catalysts electrochemically convert CO and CO2 to C1-C3 liquid products (e.g., acetate, ethanol, and propanol) at high selectivity. Electrochemical conversion of CO and CO2 to valuable chemicals is of large interest because it provides ways to recycle CO2. Using operando XAFS, combined with computational studies, we can investigate the influence of surface Ag and NDC additives and explain changes in selectivity trends. We aim to employ this state-of-the-art characterization technique to correlate the atomic bonding distance around the catalyst atomic center and coordination environment to the selectivity of our electrocatalysts towards liquid products. A better understanding of these electrochemical processes during the reaction is needed to foster further development.