In this paper, the relationship between the pore spatial structures, pore sizes, and pore types of highly ordered mesoporous CMK-based carbons (CMK-1, CMK-3, and CMK-5) and their electrochemical performance in Li-S batteries is investigated. CMK-1 has a complex spatial structure and small pores. The structure is good for limiting polysulfide in the pores, but not for rapid transfer of Li+ ions in the cell. CMK-3 and CMK-5 have similar spatial structures and pore sizes, but different pore types. Compared to the single pore structure of CMK-3, the bimodal pore structure of CMK-5 not only improves the electrolyte accessibility, but also increases the number of reaction sites, resulting in better electrochemical performance. Studying the correlation between the physical structure of carbon-based materials and their electrochemical performance in Li-S batteries will provide new insights for optimizing porous electrode materials.