Using copper (Cu) as an electrocatalyst uniquely produces multicarbon products (C₂₊-products) during the CO₂ reduction reaction (CO2RR). However, the CO2RR stability of Cu is presently 3 orders of magnitude shorter than required for commercial operation. One means of substantially increasing Cu catalyst lifetimes is through periodic oxidative processes, such as cathodic-anodic pulsing. Despite 100-fold improvements, these oxidative methods only delay, but do not circumvent, degradation. Here, we provide an interrogation of chemical and electrochemical Cu oxidative processes to identify the mechanistic processes leading to stable CO2RR through electrochemical and in situ Raman spectroscopy measurements. We first examine chemical oxidation using an open-circuit potential (OCP), identifying that copper oxidation is regulated by the transient behavior of the OCP curve and limited by the rate of the oxygen reduction reaction (ORR). Increasing O₂ flux to the cathode subsequently increased ORR rates, both extending lifetimes and reducing “off” times by 3-fold. In a separate approach, the formation of Cu₂O is achieved through electrochemical oxidation. Here, we establish the minimum electrode potentials required for fast Cu oxidation (−0.28 V vs Ag/AgCl, 1 M KHCO₃) by accounting for transient local pH changes and tracking oxidation charge transfer. Lastly, we performed a stability test resulting in a 20-fold increase in stable ethylene production versus the continuous case, finding that spatial copper migration is slowed but not mitigated by oxidative pulsing approaches alone.