A novel nanocomposite cathode consisting of sulfur and hollow‐mesoporous titania (HMT) embedded within carbon nanotubes (CNT), which is designated as S‐HMT@CNT, has been obtained by encapsulating elemental sulfur into the pores of hollow‐mesoporous, spherical TiO 2 particles that are connected via CNT. A carbon‐paper interlayer, referred to as dual functional porous carbon wall (DF‐PCW), has been obtained by filling the voids in TiO 2 spheres with carbon and then etching the TiO 2 template with a chemical process. The DF‐PCW interlayer provides a medium for scavenging the lithium polysulfides and suppressing them from diffusing to the anode side when it is inserted between the sulfur cathode and the separator. Lithium–sulfur cells fabricated with the thus prepared S‐HMT@CNT cathode and the DF‐PCW interlayer exhibit superior performance due to the containment of sulfur in TiO 2 and improved lithium–ion and electron transports. The Li–S cells display high capacity with excellent capacity retention at rates as high as 1C, 2C, and 5C rates.