Mesoporous CeO₂ catalysts (CeO₂-MOF) were synthesized by pyrolysis of Ce-MOF precursor (Ce-(1,3,5-benzenetricarboxylic acid) (H₂O)₆). Physicochemical properties of the samples were investigated by means of various techniques including XRD, SEM, TEM, BET, Raman, XPS, H₂-TPR, O₂-TPD and NH₃-TPD, and their catalytic performance were evaluated by toluene combustion compared with commercial CeO₂ (CeO₂-C) and CeO₂ prepared by precipitation method (CeO₂-P). The results show that CeO₂-MOF/350 catalyst (pyrolyzed at 350°C) presents enhanced catalytic activity for toluene oxidation with the conversion of T_10%, T_50% and T_90% at 180, 211, and 223°C, respectively (SV=20,000 mL/(g h), toluene concentration=1000 ppm). Especially for high-temperature region, CeO2-MOF/350 catalyst displays much superior ability to rapidly reach to 100% conversion compared to CeO₂-C and CeO₂-P catalysts which usually result in a much broader temperature region to achieve complete conversion of toluene. The high catalytic performance of CeO₂-MOF/350 can be reasonably ascribed to a series of better properties, such as three-dimensional penetrating mesoporous channels, larger specific surface area, smaller average grain size, higher relative percentages of Ce³⁺/Ce⁴⁺ and O_Sur/O_Latt, higher oxygen storage capacity, higher oxygen vacancy concentration, better low temperature reducibility, more active oxygen species and more acid sites. Furthermore, CeO₂-MOF/350 catalyst presented excellent resistance to H₂O deactivation and temperature change, and in situ DRIFTs study on CeO₂-MOF/350 catalyst suggests that toluene degradation is proceeded in consecutive steps via rapid transformation to aldehydic and benzoate species to finally form CO₂ and H₂O.