The industrialization and commercialization of Li–S batteries are enormously hindered by a number of defects such because the sluggish response kinetics, polysulfide shuttling and enormous quantity growth. Herein, we suggest a heteroatom doping methodology to optimize the digital construction for enhancing the adsorption and catalytic exercise of VN that’s in situ embedded right into a spongy N-doped conductive framework, thus acquiring a Co-VN/NC multifunctional catalyst as a super 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 in addition enhance the kinetics of polysulfide conversion. The density useful principle (DFT) calculations revealed that Co doping might enrich the d orbit electrons of VN for elevating the d band middle, which improves its interplay with lithium polysulfides (LiPSs) and accelerates the interfacial electron switch, concurrently. Because of this, the batteries current a excessive preliminary discharge capability of 1521 mA h g−1 at 0.1 C, good charge efficiency, and wonderful biking performances (∼876 mA h g−1 at 0.5 C after 300 cycles and ∼490 mA h g−1 at 2 C after 1000 cycles, respectively), even with a excessive areal sulfur loading of 4.83 mg cm−2 (∼4.70 mA h cm−2 at 0.2 C after 100 cycles). This well-designed work offers a very good technique to develop efficient polysulfide catalysis and additional get hold of high-performance host supplies for Li–S batteries.