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In this study, efficient sulfamethoxazole (SMX) degradation was demonstrated in a novel neutral Fered-Fenton like/oxalate (electro-Fe2+/PDS/Ox, Fered-FL/Ox) system adopting pre-anodized Ti@TiO2 cathode. Optimization of operational parameters was conducted and the whole reaction mechanism based on the critical solid-liquid interfacial reactions was explored. An efficient neutral heterogeneous-homogenous iron cycle would exist in the Fered-FL/Ox system, depending on the formation of specific C--O--Ti bonds through the inner sphere surface complex (ISSC) of Fe(C2O4)33-. It would induce ultrafast electron transfer from the cathode to the FeⅢ core, effectively accelerating the neutral Fenton-like reactions and complete mineralization of SMX with relative low dosage of ferrous catalyst and applied voltage. The result of this study is expected to supply a good altative in treating complex neutral industrial wastewaters