The construction of Co-Mn mixed metal oxides catalysts derived from bimetallic MOFs has great significance for catalytic destruction of toluene. Hence, a series of CoaMnbOx-MOFs with different physicochemical properties were successfully synthesized via pyrolysis of Co-Mn bimetallic MOFs. Attributing to the higher specific surface area, more active sites (Co3+ and Mn3+), stronger reducibility and abundant defect sites, the as-prepared Co1Mn1Ox-MOFs dispalyed an optimal catalytic performance, especially the excellent water vapor resistance. The result of the In Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy demonstrated that toluene can be degraded at relatively low temperatures (<100 °C). Benzyl alcohol, benzaldehyde, benzoic acid and maleic anhydride were the main intermediate products in toluene degradation process. This work reveals the value of bimetallic MOFs derived Co-Mn oxides for toluene oxidation and presents a novel avenue for designing mixed metal oxide catalysts with potential applications in VOCs catalytic oxidation.