Abstract: Due to the gradual development of industrial technology in China, more and more toxic and harmful refractory organic compounds are produced in the production and manufacturing process. Therefore, effective treatment of refractory wastewater is particularly important. Catalytic ozonation process is an effective means of treating refractory wastewater, but there are still some problems such as poor ozone utilization rate, low catalytic efficiency, and loss of active components of the catalyst. In this study, α-Fe₂O₃ was used as the ozone catalyst, the structure of α-Fe₂O₃ was characterized by SEM, N₂ adsorption/desorption and other methods, and a α-Fe₂O₃ catalytic ozonation system for phenol wastewater treatment was constructed to optimize the catalytic conditions and improve the treatment efficiency. The catalytic mechanism and catalyst stability were discussed in depth. The results showed that: (1) α-Fe₂O₃ were irregular spherical agglomerates with a specific surface area of 83.38 m²/g, which has a good O₃ catalytic potential. (2) The ozone dosage and pH had obvious effects on the catalytic system, but the change of α-Fe₂O₃ dosage had no obvious control on the degradation effect. Under the optimized conditions, the COD removal rate could reach 97.67% after 30 min of reaction, which was 41.33% higher than that of ozone alone. (3) After ·OH and Lewis acid sites were shielded by TBA and Na₃PO₄ in the catalytic oxidation, the COD removal rates decreased by 17.01% and 20.92%, respectively, indicating that the ·OH generated at Lewis acid sites on the catalyst surface was the main reason for the high COD removal rate. (4) α-Fe₂O₃ maintained high catalytic activity and stability in the repeated tests. After six repetitions, the COD removal rate could still reach 93.07%, and the loss rate was 1.05%. α-Fe₂O₃ shows excellent synergistic effect of ozone decomposition, has good continuous phenol removal ability and structural stability, and can provide technical reference for the efficient removal of phenolic wastewater or refractory wastewater.