A series of Co-M (M = Ce, Fe, Zr) binary oxides supported on N-doped catalysts were prepared by impregnation methods and tested for DRM reaction. Moreover, the influence of Co and Ce atomic contents in the catalysts on DRM performance was investigated. Significant enhancement of activity performance over Ce promoted 3Co-1Ce/AC-N catalyst was observed. Compared with Fe and Zr, the catalyst with 1/4 mol% of Ce showed the highest activity and was higher than the supported Co catalyst. The calcined and spent catalysts were characterized by XPS, H-2-TPR, TEM and EDX mapping studies. The characterization results demonstrated that the increase of 3Co-1Ce/AC-N reforming reactivity was attributed to the presence of Ce in Co-based catalyst, which modified the chemical states of Co-Ce composite oxide and redox properties, and increased the presence of Co2+ species, the content of chemisorbed oxygen and the oxygen mobility. Among the different Co/Ce ratio catalysts, the one with a Co/Ce molar ratio at 1 exhibited better catalytic performance. As the Ce content increases, the content of chemisorbed oxygen was further decreased. In addition, the introduction of N on the support could also affect the catalyst reduction property and interaction of Co-Ce bimetal, which would improve catalytic performance.