Confinement of sulfur and alleviation of the polysulfides dissolution are the key issues for development of high-performance lithium-sulfur (Li-S) batteries. Here, we report self-assembly sandwiches composed of zeolitic-imidazolate-frameworks (ZIF-8)-derived mesoporous carbons (ZIF-8(C)) in between reduced graphene oxide (rGO) layers, which are filled with sulfurs inside and coated with poly(3, 4-ethylenedioxythiophene) (PEDOT) outside (noted as P@rGO/ZIF-8(C)). During the synthesis process, the rGO layers stabilize the structure of ZIF-8 nanocrystals to obtain large specific surface area and high electric conductivity of mesoporous materials (rGO/ZIF-8(C)), ensuring accommodation of a large amount of sulfur and the efficient utilization of the confined sulfur. The mesoporous rGO/ZIF-8(C), PEDOT and N-doping provide physical absorption and chemical binding to the polysulfides during cycles. Consequently, the Li-S batteries with the composite cathodes exhibit the high capacity of 1308 mAh g−1 and 865 mAh g−1 at 0.2 C and 1 C, respectively, and a very low capacity fading of 0.03% per cycle after 500 reversible cycles at 1 C rate. The results indicate that the P@rGO/ZIF-8(C)-S composite cathode may offer a feasible strategy for construction of sulfur cathodes for high-performance Li-S batteries.