The effect of promoter cobalt and the sequences of adding cobalt and molybdenum precursors on the performance of sulfur-resistant methanation were investigated. All these samples were prepared by impregnation method and characterized by N2-adsorption, X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The conversions of CO for Mo-Co/Al, Co-Mo/Al and CoMo/Al catalysts were 59.7%, 54.3% and 53.9%, respectively. Among these catalysts, the Mo-Co/Al catalyst prepared stepwisely by impregnating Mo precursor firstly showed the best catalytic performance. Meanwhile, the conversions of CO were 48.9% for Mo/Al catalyst and 10.5% for Co/Al catalyst. The addition of cobalt species could improve the catalytic activity of Mo/Al catalyst. The N2-adsorption results showed that Co-Mo/Al catalyst had the smallest specific surface area among these catalysts. CoMoO4species in CoMo/Al catalyst were detected with XRD, TPR and LRS. Moreover, crystal MoS2which was reported to be less active than amorphous MoS2was found in both Co-Mo/Al and CoMo/Al catalysts. Mo-Co/Al catalyst showed the best catalytic performance as it had an appropriate surface structure, i.e., no crystal MoS2and very little CoMoO4species.