Inverse CeO₂-Co₃O₄/CuO catalysts with chrysanthemum-like morphology were prepared by the co-precipitation method, and characterized via scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), temperature-programmed reduction (H2-TPR), and N2 adsorption-desorption techniques. It is found that the filament is composed of ordered-array CuO nanocrystallites, and CeO₂ was dispersed on the outer surface of filament. The CeO₂-Co₃O₄/CuO catalyst with thin filaments can form the long periphery at the CeO₂-CuO contact interface and improve catalytic performance. Therefore, the CAT-350 catalyst with the thinnest filaments presents the highest catalytic activity among the as-prepared catalysts.