Lithium-sulfur batteries are known as the most prospective secondary batteries for their high specific capacity. Nevertheless, lithium-sulfur batteries still face difficulties such as low cycle life and shuttle effect. To solve these problems, we designed S/Core-shell CeO2/porous carbon as a kind of cathode material for Li-S batteries by template method. CA as the carbon source of the porous carbon and the core-shell CeO2 had a synergistic effect which played physical and chemical adsorption for polysulfides roles. XRD, SEM, and TEM tested the crystalline structure and core-shell structure of the material, combined with XPS to demonstrate the element valence states of Ce, C, and S. The initial discharge specific capacity of S/CS-CeO2/PC composite cathode reached 1242.6 mA h g−1 at 0.25 C. The average coulombic efficiency was 92.36 % after 500 cycles, with only 0.015 % attenuation per cycle. S/CS-CeO2/PC exhibited good electrochemical performance, cycle life, and stability.