Electrochemical oxygen reduction reaction (ORR) is a powerful tool for introducing oxygen functional groups in synthetic chemistry. However, compared with the well-developed one-electron oxygen reduction process, the applications of two-electron oxygen reduction in electrochemical synthesis have been seldom studied. We present herein our recent progress in the oxidation of α-diazoesters to α-ketoesters by in situ generated hydrogen peroxide via a two-electron oxygen reduction approach. A diverse collection of valuable α-ketoester products was obtained with moderate to high yields under an exogenous-oxidant-free and metal catalyst-free electrochemical conditions.