The AC/S composite cathode, combined with the multifunctional CNTP/TiO2 barrier, exhibits a high reversible capacity and cycling performance in Li–S batteries. AC is capable of carrying high sulfur content, greatly enhancing electron transport, and increasing the utilization of active materials. Meanwhile, the multifunctional CNTP/TiO2 barrier traps lithium polysulfides and improves the electrochemical performance of Li–S batteries in long-term cycles. Therefore, the multifunctional CNTP/TiO2 barrier is an ideal candidate for realizing long-cycle Li–S batteries. The concept may be extended to other oxides such as SiO2, Ti nO2n–1, Al2O3, and Mg0.6Ni0.4Oas well as metal-organic frameworks, which have low electrical conductivities that limit the utilization of sulfur but do possess special interactions with sulfur species.