A series of Co (10.7 wt. %)-CeO2/SiO2 catalysts with various cerium contents was prepared and evaluated. The optimized ceria-promoted catalyst exhibits good activity, high selectivity towards long chain hydrocarbons, and excellent stability. The promotion mechanism of ceria was investigated using X-ray diffraction (XRD), temperature programmed reduction (TPR), H2 temperature programmed surface reaction (H2-TPSR) and transient response technique. It is suggested that the improved catalytic performance of the catalyst modified by ceria be attributed to (1) the improvement in the dispersion of metallic cobalt and the amount of active sites for Fischer-Tropsch Synthesis (FTS), leading to an increased concentration of surface active carbon species and high selectivity towards long chain hydrocarbons; (2) the inhibition of disproportionation of CO and the removal of inactive surface carbon species.