A novel and efficient visible-light-induced C(sp2)-H/N-H cross-dehydrogenative coupling (CDC)-amination with both primary and secondary aliphatic amines at room temperature in air is developed. This photocatalytic reaction allows the direct formation of 3-aminoquinoxalin-2(1 H)-ones via CDC-amination in the absence of any external oxidant added from outside. Preliminary mechanistic studies reveal that the present reaction proceeds through a radical process.