Cu–Ce/graphene catalysts show high dispersion of metal particles and excellent activity and stability for catalytic oxidation. In this study, a hydrothermal method was used to synthesize a series of bimetallic Cu–Ce/graphene catalysts, and the effects of the proportions of Cu and Ce on CO oxidation were investigated in detail. Indispensable characterizations such as XPS, XRD, TEM, BET, and H₂-TPR were conducted to explore the effect of the Cu/Ce molar ratio and the metal valence on the activity and determine the structure–performance relationship. The results showed that bimetallic supported catalysts, such as 3Cu5Ce/graphene, 1Cu1Ce/graphene, and 5Cu3Ce/graphene, possessed significant catalytic activity. Especially, the 5Cu3Ce/graphene catalyst showed highest catalytic activity for CO oxidation, the T₁₀₀ value was 132 °C, and the apparent activation energy was 68.03 kJ mol⁻¹. Furthermore, the stability of the 5Cu3Ce/graphene catalyst was outstanding, which could be maintained for at least 12 h. Moreover, the CeO₂ particles were well crystalline with the size 5–9 nm in these catalysts, and the CuO nanoparticles were well dispersed on CeO₂ and graphene. Notably, the ratio of Cu/Ce in the catalyst was higher, the interaction between the Ce species and the graphene was stronger, and the Cu species were more easily reduced; this was beneficial for the oxidation of CO.