Designing　metal-free　catalysts　for　solar　energy　conversion　is　a　long-standing　challenge　in　semiconductor　photoredox　catalysis　(SPC).　With　visible-light-responsive　hexagonal　boron　carbon　nitride　(h-BCN)　as　a　non-metal　photocatalyst,　this　system　affords　C−H/N−H　coupling　products　with　broad　substitution　tolerance　and　high　efficiency　with　molecular　oxygen　as　the　terminal　oxidant.　The　catalyst　exhibits　remarkable　performance　for　the　selective　C−H　functionalization　of　electron-rich　arenes　to　C−N　products　(yields　up　to　95　%)　and　good　stability　(6　recycles).　Both　nitrogen　heteroarenes　and　amine　salts　are　competent　coupling　nucleophiles.　Mechanically,　the　reactive　oxygen　species　are　superoxide　anion　radical　(O2−.)　and　H2O2,　which　are　proved　by　electron　spin　resonance　(ESR)　data,　KI-starch,　and　control　experiments.　In　addition,　kinetic　isotope　effect　(KIE)　experiments　indicate　that　C−H　bond　cleavage　is　not　involved　in　the　rate　limiting　step.　This　semiconductor-based　photoredox　system　allows　for　C−H　amination　free　of　any　metals,　ligands,　strong　oxidants,　and　additives.　It　provides　a　complementary　avenue　to　C−H　functionalizations　and　enables　synthetic　applications　efficiently　in　a　sustainable　manner.　©　2019　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim