Reduced graphene oxide (RGO) wrapped metal-organic frameworks (MOFs) derived cobalt doped porous carbon polyhedrons synthesized via a carbonization process, are for the first time used for sulfur immobilizers (RGO/C–Co-S) as cathodes for high performance lithium-sulfur (Li–S) batteries. The RGO/C–Co–S cathode exhibits greatly improved electrochemical performance, showing excellent specific capacity of 949mAh g−1 at 300th cycle at a current density 0.3Ag−1, displaying enhanced rate capability with specific capacity of 772, 704 and 606mAh g−1 at current density of 0.5, 1 and 2Ag−1, respectively. The synergetic effect of MOFs-derived porous carbon, homogeneously distributed Co nanoparticles and RGO nanosheets simultaneously contributes to the confinement of sulfur species. The presence of abundant mesopores and micropores is conducive to immobilize large amounts of S species. The homogenously inlaid ultrafine Co nanoparticles can further immobilize sulfur by chemical interactions between Co and S/polysulfides. The RGO nanosheets tightly wrapped on carbon hosts act as barrier layers to prevent polysulfides from diffusing out of the matrix, further suppressing shuttle effect. The porous structure and the RGO can effectively alleviate the volume changes resulted from charge–discharge process. This design strategy can be inspiring for MOF-derived materials in energy storage applications.