The development of Li–S batteries is limited by their levels of rapid capacity decay owing to polysulfide dissolution and diffusion in organic electrolytes. We addressed this critical issue by fabricating a dual chemifunctional interlayer comprising SnO2 nanoparticles and nanoperforated graphene (NPG) that could function as a polysulfide adsorbent. The synergistic effects of SnO2 and the high-density functional groups of NPG on polysulfide capture were conceptually confirmed. NPG not only supported the adsorption of Li polysulfides but also provided pathways for simple Li-ion motion within the SnO2/NPG interlayer. A cell assembled with the SnO2/NPG interlayer displayed a high rate capability and initial discharge capacity and good reversible capacity. The excellent high-rate cycling performance of the cathode could mainly be attributed to the strong chemical bonds formed between SnO2/NPG and the polysulfides, rapid electron transfer, and optimized ion diffusion pathways derived from the well-organized structure of the composite. Synthesizing dual chemifunctional interlayers using a composite of metal oxides and NPG may lead to the development of advanced Li–S batteries with numerous practical applications in the near future.