A series of MnO_x/Cr₂O₃ composites have been prepared via the combination methods of impregnation, in situ redox precipitation and pyrolysis based on MIL-101-Cr. The physicochemical properties of catalysts have been investigated by using XRD, Raman, BET, SEM, TEM, XPS, H2-TPD and O2-TPD, and their catalytic performance has been evaluated by toluene combustion. With introduction of MnO_x into Cr₂O₃, the MnO_x/Cr₂O₃-M exhibits the obviously enhanced catalytic activity for toluene oxidation compared to commercial Cr₂O₃ or pure Cr₂O₃ pyrolyzed by MIL-101-Cr. The 14.6 wt% MnO_x/Cr2O3-M (named as 15Mn/Cr₂O₃-M) shows the highest efficiency and lowest Ea values under different SV and toluene concentrations. The catalytic durability test for toluene oxidation on 15Mn/Cr₂O₃-M presents a solid stability, where the toluene conversion maintains at ca. 85% for at least 240 h without obvious inactivation (270 °C, 1000 ppm of toluene, 20,000 mL/(g h), with 10 vol% of water vapor) and it can also maintain at conversions of 90% and 50% for at least 50 h with higher space velocity (1000 ppm of toluene, 60,000 mL/(g h)). The good durability and tolerance of 15Mn/Cr₂O₃-M are probably associated with better stability for crystal structure, oxygen vacancies, and reducibility. More MnO_x addition amount (25Mn/Cr₂O₃-M) cannot further promote catalytic performance, possibly due to excessive MnO_x existed as isolated phase with lack of strong interaction between two metal oxides. The investigation of in situ DRIFTS on 15Mn/Cr₂O₃-M confirms that surface lattice oxygen OLatt plays a crucial role in toluene combustion and the pathway for toluene combustion is via rapid transformation to aldehydic and then benzoate species and finally form CO₂ and H₂O.