The step‐order or disproportionation conversion of lithium polysulfides (LiPSs) is still a blind box in LiS batteries (LSBs) system. The cation‐doped electrocatalyst (Fe‐CoS2@HCNF) is designed through modulating electron‐surrounding situation of the central atomic d‐band to promote regional electron‐directed LiPSs reduced‐order‐transformation (especially, Li2S4Li2S). Fe‐CoS2@HCNF satisfies the requirement of mass (electron/ion) transfer reaction, quantizing as multi‐osmosis‐connected transportation channels and an all‐encompassing interior space for sulfur reduction occurring. Based on experiments and DFT calculations, the introduced Fe presents a local electron deficiency state toward regulating regional electron delocalization between Fe and Co matrix, which induces the d‐band state of the metal site, strengthening the metal 3d orbital coupling interaction with S2−of LiPSs, further guiding the order‐transformation of intermediate LiPSs. Consequently, the Fe‐CoS2@HCNF electrode has excellent electrochemical properties, performing at 3.0 C with 0.064 % capacity decay per cycle, and even maintaining super cycle stability at a high sulfur loadings. In addition, the pouch cell assembled can also reach an initial specific capacity of 1070.3 mAh g−1 at 0.1 C, which can still show good long‐term cycle stability. This work provides a valuable prospect for analyzing SRR intermediate state by regional electron flow regulation of electrocatalyst in practical LSBs.