Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction to a nucleophilic radical. However, this pathway is challenging due to the large negative reduction potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe the development of an alternative strategy to access ketyl radicals from aldehydes, which avoids the reduction pathway by instead proceeding via single-electron oxidation and desulfination of α-hydroxy sulfinates. These redox-active aldehyde adducts are generated in situ through the addition of sulfoxylate (SO 2 2−) to aldehydes and possess low oxidation potentials, thereby facilitating ketyl radical formation and circumventing the need for strongly reducing conditions. We demonstrate the application of this sulfoxylate-mediated ketyl radical formation in ketyl−olefin coupling reactions.