A copper-catalyzed four-component formal oxyaminalization of alkenes with Togni's reagent and amines using molecular oxygen as both the oxidant and oxygen source has been developed for the first time, offering a straightforward and efficient method for the synthesis of a range of structurally diverse α-oxoketene aminals. The use of cheap copper catalyst and readily available substrates, excellent functional group tolerance, broad substrate scope, mild conditions, and simple procedure are the attractive features of the strategy.