We report a novel copper-catalyzed reductive arylation of nitroarenes with arylboronic acids under LED light, enabling diarylamine synthesis under mild conditions. This photochemical approach complements traditional methods, leveraging nitroarenes' multifunctionality to activate isopropanol and facilitate arylboronic acid dehydration into reactive arylboroxines. Mechanistic studies highlight arylboroxines as key intermediates and reveal radical pathways supported by detailed experimental evidence. This facile method offers efficient C-N bond formation with broad applications in pharmaceuticals, materials science, and natural product synthesis.