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Ce-V-Ti and Ce-V-Ti/GO catalysts synthesized by the sol-gel method were used for the catalytic combustion of dioxins at a low temperature under simulating sintering flue gas in this paper. The catalytic mechanism of Ce-V-Ti catalysts modified with graphene oxides (GO) at a low temperature was revealed through X-ray diffractometer (XRD), Brunauer−Emmett−Teller (BET), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H₂-temperature-programmed reduction (H₂-TPR) and Fourier transform infrared (FTIR). During the tests, chlorobenzene (CB) was used as a model reagent since the dioxins are poisonous. The results showed that introducing GO to Ce-V-Ti catalysts can improve the specific surface area and promote the CB adsorption on the surface of catalysts. Simultaneously, the Ce-V-Ti with 0.7 wt % GO support showed the high activity with the conversion of 60% at 100 °C and 80% at 150 °C. The adsorb ability of catalysts is strengthened by the electron interaction between GO and CB through π-π bond. In the case of Ce-V-Ti catalysts, Ce played a major catalytic role and V acted as a co-catalytic composition. After GO modification, the concentration of Ce³⁺ and V⁴⁺ were enlarged. The synergy between Ce³⁺ and V³⁺ played the critical role on the low-temperature performance of catalysts under sintering flue gas.