In　this　communication　we　describe　the　oxidative　C?C　bond　formation　of　tertiary　amines　with　various　nucleophiles　under　very　mild　and　environmental　friendly　conditions　by　using　mesoporous　graphitic　carbon　nitride　(mpg-C3N4)　semiconductor　as　a　heterogeneous,　metal-free　photosensitizer　in　combination　with　visible　light　and　oxygen　as　the　terminal　oxidation　agent.　This　system　can　be　further　combined　with　proline-organocatalysis　to　achieve　oxidative　tandem　photocatalysis,　demonstrating　a　rich　cascade　of　chemical　possibilities　of　the　current　photosynthesis　system.