A visible-light-induced C-3 alkylation of quinoxalin-2(1H)-ones with N,N,N',N'-tetraalkylethylenediamine was achieved without an external photocatalyst. The mechanism showed that quinoxalin-2(1H)-ones could act as photocatalysts. The accessibility of the reagents and the green and mild reaction conditions made this protocol an alternative method to access C-3 alkylated quinoxalin-2(1H)-ones.