The electrocatalytic reduction of CO2 to chemical fuels has attracted significant attention in recent years. Among transition metals, silver shows one of the highest faradaic efficiencies for CO formation as the main reaction product; however, the exact mechanism for this conversion is not fully understood. In this work, we study the reaction mechanism of silver as a CO2 reduction catalyst using in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) during electrochemical cycling. Using ATR-FTIR, it is possible to observe the reaction intermediates on the surface of Ag thin films formed during the CO2 electroreduction reaction. At a moderate overpotential, a proton coupled electron transfer reaction mechanism is confirmed to be the dominant CO2 reduction pathway. However, at a more negative applied potential, both the COO– and the COOH intermediates are detected using ATR-FTIR, which indicates that individual proton and electron transfer steps occur, offering a different pathway than at lower potentials. These results indicate that the CO2 reduction reaction mechanism can be potential dependent and not always involving a concerted proton coupled electron transfer, opening alternative pathways to optimize efficient and selective catalysts for desired product formation.