Catalytic selective cleavage reaction of the C(sp³)–C(sp³) bond has received little attention, despite its importance in organic synthesis and biochemistry. Herein, a novel copper loaded nitrogen-rich mesoporous carbon nitride material was designed and synthesized, and utilized as a highly efficient photocatalyst for the inert C–C bond cleavage of amines under blue light irradiation. With oxygen as a benign oxidant, good to excellent yields were achieved for various functionalized amines at room temperature, even including sluggish aliphatic amines. The method may provide a cost-effective and environmentally friendly alternative for the direct oxidative cleavage of amines.