Recently, research on polyoxometalates (POMs) has gained significant momentum. Owing to their properties as electronic sponges, POMs catalystharbor substantial potential in lithium-sulfur battery research. However, POMs undergo a transformation into reduced heteropoly blue (HPB) during electrochemical reactions, which then dissolve into the electrolyte, resulting incatalyst loss. In this research, we amalgamated 18-crown-6(CR6)with K3PW12O40, (KPW), synthesized a novel POM-basedsupramolecular compound, and integrated it with graphene oxide(GO) to fabricate a multi-functional composite polypropylene (PP) separatorKPW-CR6/GO/PP. The crown ether array was employed to immobilizePOM and construct ion transport channels, thereby enhancing the Li+migration rate and capturing polysulfides. Subsequently, leveraging the stable structure and redox properties of POM, the polysulfide is catalyzed to transform and inhibit the shuttle effect, thereby protecting the Lianode.The lithium-sulfur batteries with the Crown ether-POM supramolecular compoundseparators, exhibit enhanced capacity and stability (1073.3mAh g-1at 1.0C, and 81.5% retention rate after 250 cycles). Thebattery (Sloading:3.2 mg cm-2) presents an initial specific discharge capacity of 543.4 mAh g-1at 0.5 C, with 89.8% of the capacity retained after 160 cycles.Thisunderlinesthe practical application potential of Crown ether-POM supramolecular materials in Li-S batteries.