Abstract: In the process of waste incineration, a large amount of chlorinated volatile organic pollutants (CVOCs) such as chlorobenzene and persistent organic pollutants (POPs) such as PCDD/Fs are generated. The emission of CVOCs will lead to photochemical smoke and the greenhouse effect. PCDD/Fs can exist in soil for a long time, causing serious consequences such as carcinogenesis and teratogenesis to the human body. Catalytic degradation technology has significant advantages in PCDD/Fs treatment, which can completely destroy and decompose organic pollutants and convert them into CO₂, H₂O, HCl and other products. Transition metal oxide catalysts based on VO_x/TiO₂ have been widely used in the treatment of flue gas CVOCs and PCDD/Fs. The V=O group in VO_x plays the role of nucleophilic adsorption of PCDD/Fs. Adding the second active component MoO_x to vanadium-based oxide can improve the catalytic activity of the catalyst. In this study, a series of powder catalysts of VO_x-MoO_x/TiO₂ for catalytic degradation of CVOCs were prepared by wet impregnation method. The synthesis method, catalytic characterization and performance test results of VO_x-MoO_x/TiO₂ catalyst were analyzed. The influence mechanism of reaction temperature on the catalytic degradation rate of chlorobenzene (CB) and PCDD/Fs was discussed, providing reference for expanding PCDD/Fs catalytic technology. The results show that VO_x-MoO_x/TiO₂ catalyst has excellent catalytic activities, which is attributed to its abundant surface catalytic active sites, good dispersion of active components, low initial reduction temperature, high active oxygen content, large specific surface area, and less particle agglomeration. Through a series of experiments, the formulation of 5%VO_x-5%MoO_x/TiO₂ (denoted as ‘V5-Mo5-Ti’, the mass fraction of VO_x and MoO_x respectively accounts for 5% and the mass fraction of TiO₂ accounts for 90%) with the highest catalytic activities was developed, which showed excellent catalytic activities on both CB and PCDD/Fs at the low temperature of 150 ℃. The conversion rate of V5-Mo5-Ti at low temperature was increased as the initial concentration and gas hourly space velocity (GHSV) increased. When the initial concentration of CB was 150×10⁻⁶ and the GHSV was 10,000 h⁻¹, the conversion rate of CB by V5-Mo5-Ti was 54.0% at 150 ℃ and was close to 100% at 300 ℃. At low-temperature (150 ℃), the removal rate of PCDD/Fs was higher than 86%, and the catalytic rate was higher than 74%. The research shows that the catalytic removal rate and degradation rate of PCDD/Fs by VO_x-MoO_x/TiO₂ catalyst increased with the increase of reaction temperature, attributing to the accelerated oxidation cycle rate of V⁵⁺ and V⁴⁺ in V₂O₅ and Mo⁶⁺ and Mo⁴⁺ in MoO₃.