The residues of daily-used antibiotics are difficult to be removed and very harmful to the environment. Herein, FeO@FeP heterostructure was constructed by surface phosphorization of hematite (α-Fe₂O₃) synthesized via a facile hydrothermal method for efficient photo-Fenton degradation of antibiotic norfloxacin (NOR). Compared with the bare α-Fe₂O₃, the FeO@FeP heterostructure exhibits much-enhanced photocatalytic Fenton-like performance, with NOR degraded by 75% within 5 ​min by sunlight-driven photo-Fenton reactions. It was suggested that the surface phosphorization-derived metallic FeP overlayer could accelerate the separation and migration of photogenerated charge carriers in α-Fe₂O₃, which benefits the generation of •OH and O₂^•− reactive radicals from photo-Fenton reaction and thus give rise to the great enhancement in NOR degradation activity. This study displays an alternative strategy of surface engineering to design novel heterostructured materials for the efficient photo-Fenton treatment of wastewater containing antibiotic residues as well as other organic pollutants.