Fenton reaction is regarded as a potential treatment for antibiotics removal, but challenges remain due to the sluggish reaction kinetics of Fe(III) reduction and incomplete degradation from insufficient active substance. Distinguished from traditional Fe(Ⅱ) regeneration techniques, this work focuses on utilizing the aliovalent redox pairs and built-in electric field to induce photo-excited electrons to cross the material interface and achieve Fe(III) reduction (heterogeneous regeneration). Herein, oxygen-deficient CeO₂ particles are anchored on metal-organic frameworks (MIL-88A) and thus constitute the heterojunction with enhanced photoelectric properties, accelerating the directional charge transfer. Consequently, the synthesized MIL-88A/CeO₂(OV) composite can degrade 95.76% of oxytetracycline within 60 min in photo-Fenton reaction and maintain a high mineralization rate (75.33%) after 4 cyclic tests. Furthermore, the charge transfer mechanisms of Fe cycle and antibiotics mineralization are both unveiled via experiment results and theorical calculation. This work proposes a new paradigm for constructing self-sufficient photo-Fenton catalytic system for efficient and sustainable removal of polycyclic antibiotics.