The copper-catalyzed alpha-amination of carbonyl compounds using nitrosoformate intermediates as the electrophilic source of nitrogen is reported: The reaction merges aerobic oxidation and Lewis acid catalysis. The scope of the reaction is broad in terms of both the N-substituted hydroxylamines and the beta-ketoesters. The new methodology harnesses the power of nitrosoformate intermediates and demonstrates their potential as a viable electrophilic source of nitrogen in alpha-functionalization reactions.