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This paper reported the degradation of 4-CP wastewater by a novel photocatalysis oxidation system--UV/Fe2+/air system, in which air was used as a cheap oxidant that reacted with the excitation state of organics to form H2O2 under the UV light. The formed H2O2 reacted with the added ferrous ion to form Fenton reaction and led to the quick degradation of organic pollutants. It was found that 4-CP could be completely removed within 40 min. The degradation of 4-CP in the UV/Fe2+/air system was superior to the conventional UV/Fenton system (the initial concentration of H2O2 was 22 mg-L-1). UV/Fe2+/air is an effective and cheap method for treatment of the organics that can be excited by UV light.