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Catalysts based on inexpensive and abundant transition metals are necessary for effective environmental remediation. In this study, a series of CuMn-CeO2 catalysts is synthesized by a simple coprecipitation method. The properties of the as-prepared catalysts are characterized by X-ray diffraction, Brunauer–Emmett–Teller analysis, scanning electron microscopy–energy-dispersive spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The introduction of dopants results in rougher surfaces with greater surface areas and pore volumes as well as more surface defects. Furthermore, the dopant-added catalysts exhibit higher activities for benzene oxidation, as the temperature required for 90% benzene removal with Cu4Mn1-CeO2 (656 K) was 231 K lower than that required with CeO2. The superior performance of the dopant-added CeO2 catalyst is attributed to the generation of defect-rich surfaces due to the isomorphous substitution of Cu and Mn in the crystal lattice of CeO2.