Although TiO₂-based photocatalysts have achieved great successes for the degradation of organic pollutants, the complete removal of antibiotics is hard to be realized because of its unique macromolecular ring structure under solar-light irradiation. Herein, this work demonstrates the rational design of the hierarchical hollow SiO₂-Fe₂O₃@TiO₂ (SFT) photocatalyst by introducing spatially confined Fe₂O₃ as a modifier of TiO₂, in which inner SiO₂ serves as a carrier to support and disperse Fe₂O₃ in order to obtain small size of Fe₂O₃ (2–6 nm), while outer TiO₂ acts as a bounding wall to protect Fe₂O₃ from aggregation and abscission. The as-synthesized SFT photocatalyst not only can overcome easy corrosion, dissolution and deactivation of Fe₂O₃ during the photoreaction process, but also can substantially enhance the adsorption of antibiotics because of its hierarchical hollow structure, facilitating the separation of electron-hole pairs and prolonging the trapping of incident light. Therefore, the SFT photocatalyst manifests the complete removal of antibiotics under simulated solar light irradiation. The intermediates of antibiotics were analyzed by liquid chromatography-mass spectrometry (LC/MS) and the possible degradation pathway was proposed accordingly. Besides, SFT photocatalyst exhibits an excellent recyclability due to confinement effect. Especially, the as-synthesized SFT also achieves the 100% degradation rate of antibiotics under natural sunlight irradiation, efficiently overcoming the incomplete removal of antibiotics for many previous TiO₂-based photocatalysts.