A series of Mn/Ce-based bimetal-organic frameworks, recorded as MCDx (x = 1, 2, 4, 6), were prepared by a solvothermal synthesis method to explore their effects and performance in the synergistic catalysis of toluene under the irradiation of non-thermal plasma. The catalytic properties of different manganese loadings in MCDx for degradation of toluene were investigated. The microphysical structures of the material were analyzed by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The results showed that a MCDx coupling with non-thermal plasma can greatly improve the degradation efficiency, the energy efficiency and the CO2 selectivity, and could also significantly reduce the generation of O3 in the by-products. Among the test samples, MCD6 with Mn:Ce = 6:1 (molar ratio) showed the best catalytic performance and stability, exhibited toluene catalytic efficiency 95.2%, CO2 selectivity 84.2% and energy efficiency 5.99 g/kWh, and reduced O3 emission concentration 81.6%. This research provides a reference for the development and application of synergistic catalysis based on bimetal-organic frameworks and non-thermal plasma in the reduction of industrial volatile organic compounds.