Severe shuttle effect of soluble polysulfides and sluggish redox kinetics have been thought of as the critical issues hindering the extensive applications of lithium‐sulfur batteries (LSBs). Herein, one‐dimensional boron nitride (1D BN) fibers with abundant pores and sufficient N‐vacancy defects were synthesized using a thermal crystallization following a pre‐condensation step. The 1D structure of BN facilitates unblocked ions diffusion pathways during charge/discharge cycles. The embedded pores within the polar BN strengthen the immobilization of polysulfides via both physical confinement and chemical interaction. Moreover, the highly exposed active surface area and intentionally created N‐vacancy sites substantially promote reaction kinetics by lowering the energy barriers of the rate‐limiting steps. After incorporating with conductive carbon networks and elemental S, the as‐prepared S/Nv‐BN@CBC cathode of LSBs deliver an initial discharge capacity of up to 1347 mAh g‐1 at 200 mA g‐1, while maintaining a low decay rate of 0.03% per cycle over 1000 cycles at 1600 mA g‐1. This work offers an effective strategy to mitigate the shuttle effect and highlights the significant potential of defect‐engineered BN in accelerating the reaction kinetics of LSBs.

N‐Vacancy Enriched Porous BN Fibers for Enhanced Polysulfides Adsorption and Conversion in High‐Performance Lithium‐Sulfur Batteries