Lithium–sulfur batteries (LSBs) exhibit high theoretical specific capacities, abundant resource reserves, and low costs, making them promising candidates for next-generation lithium-ion batteries (LIBs). However, significant challenges, such as the shuttle effect and volume expansion, hinder their practical applications. To address these issues, this study introduces a unique intermediate layer comprising N-doped carbon nanofiber/TiO2/diatomite (NCNF/TiO2/DE) from the perspective of membrane modification. The intermediate layer comprises nitrogen-doped titanium dioxide/carbon nanofiber (NCNF/TiO2) materials, with diatomite filling the fiber gaps. This forms a three-dimensional (3D) conductive network that provides ample space for sulfur volume expansion and numerous adsorption active sites, thereby accelerating electrolyte penetration and lithium-ion diffusion. These features collectively contribute to the outstanding electrochemical performance of the battery. At 0.1 C, the NCNF/TiO2/DE-800-coated separator battery achieved a first-cycle discharge specific capacity of 1311.1 mAh g−1, significantly higher than the uncoated lithium–sulfur battery (919.6 mAh g−1). Under varying current densities, the NCNF/TiO2/DE-800 material demonstrates good electrochemical reversibility and exhibits high lithium-ion diffusion rates and low charge-transfer resistance. Therefore, this study provides an advanced intermediate layer material that enhances the electrochemical performance of lithium–sulfur batteries.