The shuttle effect induced by soluble lithium polysulfides (LiPSs) is known as one of the crucial issues that limit the practical applications of lithium-sulfur (Li-S) batteries. Herein, a titanium dioxide nanoparticle embedded in nitrogen-doped porous carbon nanofiber (TiO₂@NCNF) composite is constructed via an interface-induced polymerization strategy to serve as an ideal sulfur host. Under the protection of the nanofiber walls, the uniformly dispersed TiO₂ nanocrystalline can act as capturing centers to constantly immobilize LiPSs towards durable sulfur chemistry. Besides, the mesoporous microstructure in the fibrous framework endows the TiO₂@NCNF host with strong physical reservation for sulfur and LiPSs, sufficient pathways for electron/ion transfer, and excellent endurance for volume change. As expected, the sulfur-loaded TiO₂@NCNF composite electrode presents a fabulous rate performance and long cycle lifespan (capacity fading rate of 0.062% per cycle over 500 cycles) at 2.0 C. Furthermore, the assembled Li-S batteries harvest superb areal capacity and cycling stability even under high sulfur loading and lean electrolyte conditions.