An efficient and novel visible-light-induced oxo-amination of terminal alkenes for the construction of α-amino ketones with easily accessible and green O2 as the oxygen source has been developed. The transformation possesses the advantages of operational simplicity, a broad substrate scope, high atom economy, and mild reaction conditions. The mechanistic studies reveal that an energy transfer process probably occurs in the initial stage, and the reaction proceeds via β-scission of the alkoxyl radical species.