Atom-economical C-C coupling between imines and a C1 source could provide alpha-aminoaldehyde derivatives. Nevertheless, such a coupling has rarely been achieved owing to the lack of appropriate nucleophilic C1 sources. In this study, photocatalytic synthesis of alpha-aminoacetals was achieved via decarboxylative coupling of imine and 2,2-diethoxyacetic acid using a nonstoichiometric amount of a radical initiator. Various functional groups were compatible, providing efficient one-step access to diversely functionalized alpha-aminoacetals, which provides a promising platform for further research.