Co-Ni bi-metallic catalysts supported on Ce-Al2O3 (CA) were prepared with different Co ratios, and the catalytic behaviors were assessed in the n-decane steam reforming reaction with the purpose of obtaining high H2 yield with lower inactivation by carbon deposition. Physicochemical characteristics studies, involving N2 adsorption-desorption, X-ray diffraction (XRD), H2-temperature-programmed reduction (H2-TPR), NH3 temperature programmed reduction (NH3-TPD), SEM-energy dispersive spectrometer (EDS), and transmission electron microscope (TEM)/HRTEM, were performed to reveal the textural, structural and morphological properties of the catalysts. Activity test indicated that the addition of moderate Co can improve the hydrogen selectivity and anti-coking ability compared with the mono-Ni/Ce-Al2O3 contrast catalyst. In addition, 12% Co showed the best catalytic activity in the series Co-Ni/Ce-Al2O3 catalysts. The results of catalysts characterizations of XRD and N2 adsorption-desorption manifesting the metal-support interactions were significantly enhanced, and there was obvious synergistic effect between Ni and Co. Moreover, the introduction of 12% Co and 6% Ni did not exceed the monolayer saturation capacity of the Ce-Al2O3 support. Finally, 6 h stability test for the optimal catalyst 12%Co-Ni/Ce-Al2O3 demonstrated that the catalyst has good long-term stability to provide high hydrogen selectivity, as well as good resistance to coke deposition.