The water pollution issue triggered by antibiotic was a great challenge facing humanity, and it was necessary to develop an effective remediation technique. In this work, Fe2O3/Co3O4 composite with internal electric field was fabricated by a simple method. The presence of internal electric field reduced the interfacial resistance and facilitated the charge transfer, so stimulating the electron transport during reaction process. With the inducement of electrostatic force based on internal electric field, two active areas (namely electron-rich region and electron-deficient region) were formed at Fe2O3/Co3O4 composite. The electron-deficient active area (namely Co3O4 component) can oxidize peroxymonosulfate (PMS) to produce SO5•-, further turning into 1O2. In the meantime, the Fe2O3 component as electron-rich active area provided electrons to achieve the Fe-O-O heterolysis, then generating high-valent metal complexes. As predicted, the Fe2O3/Co3O4-driven PMS system displayed excellent ability to remove ofloxacin. Furthermore, the micro reactor loaded with Fe2O3/Co3O4 composite exhibited satisfactory performance in treating the wastewater containing ofloxacin. All in all, the effects of internal electric field on PMS activation are investigated in depth, which provided a valuable reference for future research.