Abstract A visible‐light‐promoted strategy for the decarboxylative C‐3 carbamoylation of quinoxalinone scaffolds is developed. This approach initiates through the formation of an EDA complex between oxamic acid and quinoxalinone. Successive SET and decarboxylative carbamoylation construct the C−C bond. This method utilizes aerial oxygen as the green oxidant and eradicates the process from the use of external photocatalysts and transition metals. Detailed synthetic and photophysical studies enlighten the reaction pathway.