The industrialization and commercialization of Li-S batteries are significantly hindered by a number of defects such because the sluggish response kinetics, polysulfide shuttling and enormous quantity growth. Herein, we suggest a heteroatom doping technique to optimize the digital construction for enhancing the adsorption and catalytic exercise of VN that in situ embedded into spongy N-doped conductive framework, thus acquiring a Co-VN@NC multifunctional catalyst as a really perfect sulfur host. The synthesized composite has each the distinctive structural benefits and the synergistic impact of cobalt, VN, and nitrogen-doped carbon (NC), which not solely enhance the polysulfide anchoring of the sulfur cathode but additionally enhance the kinetics of polysulfide conversion. The density perform concept (DFT) calculations revealed that Co doping might enrich the d orbit electrons of VN for elevating d band middle, which enhance its interplay with lithium polysulfides (LiPSs) and speed up the interfacial electronics switch, concurrently. Consequently, the batteries current a excessive preliminary discharge capability of 1521 mAh g-1 at 0.1 C, good price efficiency, and wonderful biking performances (∼876 mAh g-1 at 0.5 C after 300 cycles and ∼490 mAh g-1 at 2 C after 1000 cycles, respectively), even with a excessive areal sulfur loading of 4.83 mg cm-2 (∼4.70 mAh cm-2 at 0.2 C after 100 cycles). This well-designed work supplies a very good technique to develop efficient polysulfides catalysis and additional receive high-performance host supplies for Li-S batteries.