Aiming at the problem of low mass transfer efficiency of ozone existed in traditional reactor, the high gravity technology of rotating packed bed (RPB) coupled with advanced oxidation method of O₃/Fe(Ⅱ), (RPB-O₃/Fe(Ⅱ)) was used for deep oxidation degradation of aniline (AN) wastewater. The effects of high gravity factor β, dosage of catalyst Fe(Ⅱ), concentration of O₃, pH value of system and initial concentration of AN on the degradation rate of AN and removal efficiency of total organic carbon (TOC) were studied. The intermediates of AN degradation process were analyzed by liquid chromatograph-mass spectrometer (LC-MS). The degradation mechanism of AN was investigated. Results show that increasing of high gravity factor is beneficial to the deep degradation of AN wastewater. The pH value of the system can affect the direct and indirect reactions of ozonation and the existence form of catalyst Fe(Ⅱ). and the RPB-O₃/Fe(Ⅱ) system broadens the pH range for O₃ use. The increase of ozone concentration is beneficial to improving the efficiency of AN degradation but the utilization efficiency of ozone decreases. When high gravity factor is 100, Fe(Ⅱ) concentration 0.8 mmol·L^-1, O₃ concentration 36 mg·L^-1, pH 3 and initial concentration of AN 200 mg·L^-1, the AN removal efficiency reaches 100% in 12 min, and TOC removal efficiency is 73% in 60 min.The intermediates of AN oxidation degradation process mainly are nitrobenzene, p-benzoquinone, maleic acid and oxalic acid. The possible pathway to deduce the catalytic oxidation degradation of AN by O₃ is described.