To realize efficient low-temperature catalytic o-xylene oxidation, MOF-derived CeO2-X catalysts were prepared via the pyrolysis of MOF precursors with different ratios of cerium nitrate to trimesic acid. Among the synthesized catalysts, the bouquet like CeO2-1 exhibited the best activity with T50 and T90 of 156 and 198 °C and the lowest activation energy of 60.67 kJ·mol-1 (WHSV= 48 000 mL·g-1·h-1, o-xylene concentration = 500 ppm). o-Xylene was completely mineralized, and no change in conversion efficiency or CO2 yield was found at 5 vol % H2O for over 50 h. The rich active oxygen species (XPS: Osur/Olatt = 0.69) and abundant oxygen vacancies (Raman: ID/IF2g = 0.036) of CeO2-1 made crucial contribution to its superior catalytic activity. The O2-TPD and H2-TPR results confirmed that CeO2-1 had more surface active oxygen and better mobility of bulk oxygen. Moreover, the reaction routes under different atmospheres were probed through in situ DRIFTS, in which oxygen vacancy played a key role in promoting the adsorption and activation of molecular oxygen and facilitating the migration of the bulk lattice oxygen.