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Porous ceria nanorods modified with Fe or Co were prepared via a hydrothermal method. The structural properties, catalytic activities for the total oxidation of propane, and catalytic mechanisms of these materials were systematically investigated by X-ray diffraction, Raman spectroscopy, N2 adsorption–desorption, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, catalytic activity measurements and in situ Fourier transform infrared spectroscopy. Co-modified ceria exhibited the best catalytic activity during propane oxidation as well as enhanced reducibility due to the synergistic interactions between the Co and the CeO2 support. Variations in the activating ability and reducibility of the catalysts resulted in the formation of distinctive intermediates during the catalytic process, and this explained the observed differences in catalytic performance.