Although lithium-sulfur (Li-S) batteries deliver high specific energy densities, lots of intrinsic and fatal obstacles still restrict their practical application. Electrospun carbon nanofibers (CNFs) decorated with ultrafine TiO2 nanoparticles (CNF-T) were prepared and used as a multifunctional interlayer to suppress the volume expansion and shuttle effect of Li-S battery. With this strategy, the CNF network with abundant space and superior conductivity can accommodate and recycle the dissolved polysulfides for the bare sulfur cathode. Meanwhile, the ultrafine TiO2 nanoparticles on CNFs work as anchoring points to capture the polysulfides with the strong interaction, making the battery perform with remarkable and stable electrochemical properties. As a result, the Li-S battery with the CNF-T interlayer delivers an initial reversible capacity of 935 mA h g(-1) at 1 C with a capacity retention of 74.2% after 500 cycles. It is believed that this simple, low-cost and scalable method will definitely bring a novel perspective on the practical utilization of Li-S batteries.