Catalytic combustion is a well-established way to remove the pollution of volatile organic compounds (VOCs), and the highly active catalyst is the key issue of this process. Herein, a series of sponge-like ternary mixed oxide were prepared by a facile surfactant modified coprecipitation approach. The structure properties were characterized via BET, XRD, Raman, TEM, EDS, H-2-TPR, and XPS techniques. It was found that the Cu content significantly influences the catalytic activity in toluene combustion. The CMC-2 (Cu:Mn:Ce = 1:5:5) showed the best catalytic performance under the air atmosphere, and the complete conversion of toluene was achieved at 240 C-omicron. The characterization reveals that a proper amount of Cu facilitates the incorporation of highly reducible Mn4+ into ceria lattice to form sponge-like MnCeOx solid solution structures. Such promotion effect of copper can improve the redox behavior, produce large amounts of O-alpha at the interface of CuOx/MnCeOx both of which benefit the toluene combustion at low temperature. The findings of this work highlight the importance of Cu in preparation of the active MnOx CeO2 catalyst for VOcs combustion.