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Catalytic ozonation with metal oxides is of interest for advanced water treatment technology. The amount of active oxygen-containing radicals produced is a primary objective of this process. Fe₂O₃ is a widely used catalyst because of its high performance. In this study, Fe₂O₃/SBA-15 was synthesized and characterized. The results revealed that Fe₂O₃/SBA-15 was a nano-/mesoporous material with high-order hexagonal array structures and exhibited greater catalytic performance than Fe₂O₃ in ozonation processes. To investigate the role of the Fe₂O₃/SBA-15 surface in O₃ decomposition, the kinetic constant was measured, and the interfacial reactions were discussed. Compared with Fe₂O₃, Fe₂O₃/SBA-15 significantly increased the formation of hydroxyl radicals (•OH) and the efficient utilization of O₃ in the catalytic O₃ decomposition process. The SBA-15 support decreased the O₃ self-decomposition rate during catalytic ozonation with Fe₂O₃/SBA-15, which resulted in increased formation of •OH via the reaction between O₃ and Fe₂O₃. From a practical point of view, Fe₂O₃/SBA-15 is an efficient green ozonation catalyst for water treatment.