Mesostructured CuMnCeO x catalysts were prepared and tested in chlorobenzene destruction. Mn and Cu phases enter CeO2 matrix with a fluorite-like structure to form Cu–Mn–O–Ce solid solution. Both synthesis protocol and metal-doping content affect the metal state, reducibility, and oxygen distribution of composites. The c0.15c0.15c0.7 sample exhibits the highest activity with 90 % of chlorobenzene oxidized at around 250 °C. Enhanced oxygen concentration and mobility, and abundant oxygen vacancy promote the desorption of adsorbed Cl, which guarantees the superior stability of CuMnCeO x . Incorporation of CuO and MnO x effectively inhibits the formation of organic byproducts, such as phenolates, maleates, and o-benzoquinone, especially at elevated temperatures.