A facile and efficient quinoline-fused 4-benzo[][1,4]oxazine has been successfully fabricated through an oxidative -arylation, Pd-catalyzed double -arylation of 4-hydroxyquinoline derivatives and trivalent aryl iodides. Diversified fused heterocycles could be easily constructed in overall high isolated yields with great substrate scope. The afforded heteroatom-"doped" phenoxazine demonstrated high molar absorptivities and excellent stability and redox reversibility. These phenoxazine analogues therefore could be utilized as promising catalysts in the photoredox catalyzed perfluoroalkylation of heteroarenes and photopromoted radical polymerization (OATRP).