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Catalysts for the efficient catalytic decomposition of ozone to generate reactive free radicals to oxidize pollutants are needed. The graphite-supported CeO₂ catalyst was optimally prepared, and its activity in ozonation was evaluated using the degradation of diethyl phthalate (DEP) as an index. The stability of CeO₂/graphite catalyst and the influence of operating conditions on its catalytic activity were investigated, and the mechanism of CeO₂/graphite catalytic ozonation was analyzed. CeO₂/graphite had the highest catalytic activity at a Ce load of 3.5% and a pyrolysis temperature of 400 °C with the DEP degradation efficiency of 75.0% and the total organic carbon (TOC) removal efficiency of 48.3%. No dissolution of active components was found during the repeated use of CeO₂/graphite catalyst. The ozone dosage, catalyst dosage, initial pH, and reaction temperature have positive effects on the DEP degradation by CeO₂/graphite catalytic ozonation. The presence of <i>tert</i>-butanol significantly inhibits the degradation of DEP at an initial pH of 3.0, 5.8, or 9.0, and the experimental results of the ^•OH probe compound <i>p</i>CBA indicate that the CeO₂/graphite catalyst can efficiently convert ozone into ^•OH in solution. The DEP degradation in the CeO₂/graphite catalytic ozonation mainly depends on the ^•OH in the bulk solution formed by ozone decomposition.