摘要： 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.