In our work, metal organic framework (MOFs)-derived MnCeOx catalysts were synthesized by different calcination temperatures. Effect of calcination temperature was characterized by thermogravimetric (TG), X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), N2 adsorption-desorption (BET), X-ray photoelectron spectroscopy (XPS) and temperature programmed H2 reduction (H2-TPR). Performance testing of toluene found that 1Mn1Ce-300 showed the best performance (T90 = 244 °C), good durability and reliable water resistance in catalyzing toluene. The better catalytic performance of 1Mn1Ce-300 was attributed to the higher molar ratios of Ce3+/Ce4+, Mn3+/Mn4+ and Oads/Olatt, more adsorbed oxygen, surface oxygen vacancy and better low-temperature reduction. In situ diffuse reflectance, infrared Fourier transform spectroscopy (in-situ DRIFTS) and thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) proved that benzoic acid and benzene were the main intermediates. This work was instructive for the preparation of metal oxide catalysts by pyrolysis of MOFs.