This study confirmed the feasibility of natural limonite working as the iron catalyst for the PNP wastewater treatment in the BES-Fenton system. After the start-up period of the BES-Fenton systems, air and limonite powder were injected into the cathode chamber as the original materials for manufacturing Fenton reagents of H2O2 and Fe(II) respectively. The experiment parameters like pH, external resistance, limonite dosage and initial PNP concentration were investigated in this research. The removal efficiency of PNP (0.25 mM) could achieve 96% in 6 h under the optimal experimental conditions. A limonite dosage of 112 mg per 50 ml of PNP solution at 0.25 mM concentration each time could sustain 7 cycles of the BES-Fenton system operation with PNP removal efficiency >94%. This study suggests an efficiency and cost-effective approach for the PNP removal by using the natural limonite as the iron catalyst of the BES-Fenton system. (c) 2013 Elsevier B.V. All rights reserved.