Herein, we introduce polymer nanofibers of TiO2@NiCo-LDH as interlayers into Li-S batteries. From 0 to 60 °C, the interlayers can deliver high sulfur utilization, an outstanding rate capability, and excellent cycling life. High-temperature excitation makes it easier for the valence band electrons of TiO2 to transition to the conduction band. The electron-hole pairs formed on the surface combine with the ether group of 1,3-dioxolane in the electrolyte, which greatly reduces the decomposition and volatilization rates of the electrolyte, ensuring Li-S batteries with good cycle performance at high temperatures. The capacity can stabilize at 798.6 mAh g-1 after 100 cycles at 60 °C and 1C, and the battery can provide a capacity higher than 323.2 mAh g-1 at 0 °C. Simultaneously, the lithium metal symmetrical battery with a functional separator can be continuously cycled for 1800 and 750 h without a short circuit at the current densities of 0.65 and 1.63 mA cm-2, respectively.