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With visible\u2010light irradiation, cobaloxime not only oxidizes phosphine oxides to form phosphorus radicals (P\u2010radicals) for a subsequent reaction with radical acceptor isocyanides or heteroaromatics, but also combines the radical intermediate with <jats:italic>\u03b2<\/jats:italic>\u2010H elimination, thereby producing phosphorylated heteroaromatics with only H<jats:sub>2<\/jats:sub> or CH<jats:sub>4<\/jats:sub> as byproduct. Phosphine oxides with dialkyl, alkylaryl, and diaryl substituents could be directly transformed into phosphorylated phenanthridines, benzothiazoles, isoquinolines, and common heteroaromatics. This catalytic system features extremely mild conditions, broad substrate scope and good to excellent yields. 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