For VOCs oxidation technology, significant room for enhancement still exists in terms of catalytic performance of commonly used transition metal oxide-based catalysts. In this work, we designed MnFeOx oxides catalysts by using in situ pyrolysis of MnFe bimetallic MOF-74 as efficient and stable catalysts for toluene oxidation and this bimetallic framework was synthesized by metal doping. The preferred Mn2Fe3Ox-500 (Mn/Fe molar ratio of 2:3, calcination T=500 °C) catalyst exhibited excellent catalytic activity and stability towards toluene which was significantly superior the control MnOx-500 catalyst. Under simulated industrial real-exhaust conditions, the Mn2Fe3Ox-500 catalyst maintained better resistance at higher air velocities, in addition to exhibiting excellent stability and good water resistance. The superior toluene oxidation activity of Mn2Fe3Ox-500 catalyst can be associated with its high reducibility of metal active species, abundance of oxygen species, and the well dispersion of Fe2O3 and MnOx species. In addition, suggested potential degradation pathways for toluene over the Mn2Fe3Ox-500 catalyst. For the exhaust gas purification industry, this work will be beneficial in exploring the mechanistic level of MOF materials in the field of VOCs removal.