The high-energy LiS battery suffers from poor cycling performance due to the shuttle effect of the polysulfides. Strategies must be adopted to suppress the diffusion of polysulfides into the electrolyte in LiS battery. In this work, for the first time, we adopt hydrophilic carbon paper anchored by hierarchically porous cobalt disulfides as the interlayer for capturing polysulfides through physical absorption and chemical bonding. Hierarchical pores can physically adsorb polysulfides, and moreover cobalt disulfide can trap the polysulfides by forming strong chemical interaction. The sulfur-graphene composite with a sulfur content of 70.5% delivers a high initial capacity of 1239.5 mAh g−1 at 0.2 C and retains a reversible capacity of 818 mAh g−1 after 200 cycles. In spite of a little capacity contribution by the insertion of lithium ions into cobalt disulfide for the initial cycles, it disappears in the subsequent cycling. Therefore, the as-developed porous transition metal disulfides on carbon paper as the interlayer could significantly enhance the cycling performance of LiS batteries.