Lithium–sulfur (Li–S) batteries are hindered by the shuttle effect and the sluggish redox kinetics of polysulfides. In this study, topological insulators (TIs) Bi2Te3−x with abundant Te vacancies embedded in N and B co‐doped carbon nanorods (Bi2Te3−x@NBCNs) are synthesized and used as sulfur host composites for high‐performance Li–S batteries. Bi2Te3−x@NBCNs effectively enhance the intrinsic conductivity, strengthened the chemical affinity, and accelerated the redox kinetics of polysulfides. 1D carbon nanorods with N and B co‐doped heteroatoms endowed with abundant polar sites improve the chemical affinity of polysulfides, while the embedded Bi2Te3−x nanoparticles further promote the nucleation and electrodeposition of Li2S2/Li2S. In situ Raman spectroscopy confirms that Bi2Te3−x@NBCNs effectively reduced cathode‐side accumulation of polysulfides and suppressed the shuttle effect. Owing to the extraordinary synergistic effects of rich heteroatom polar sites and conductive topological surface states, Bi2Te3−x@NBCN‐based cells exhibit a high initial specific capacity of 1264 mAh g−1 at 0.2 C and ultra‐long lifetime (>1000 cycles, with a degradation rate of 0.02% per cycle at 1.0 C). The fundamental insights offered by this work are likely to enable improvement of the electrochemical performance of Li–S batteries based on TI materials.