Lithium−sulfur (Li−S) batteries are considered as promising candidates for next-generation batteries due to their high theoretical energy density. However, the practical application of Li−S batteries is still hindered by several challenges, such as the polysulfide shuttle and the growth of lithium dendrites. Herein, we introduce a bifunctional K 3 PW 12 O 40 / graphene oxide-modified polypropylene separator (KPW/GO/PP) as a highly effective solution for mitigating polysulfide diffusion and protecting the lithium anode in Li−S batteries. By incorporating KPW into a densely stacked nanostructured graphene oxide (GO) barrier membrane, we synergistically capture and rapidly convert lithium polysulfides (LiPSs) electrochemically, thus effectively suppressing the shuttling effect. Moreover, the KPW/GO/ PP separator can stabilize the lithium metal anode during cycling, suppress dendrite formation, and ensure a smooth and dense lithium metal surface, owing to regulated Li + flux and uniform Li nucleation. Consequently, the constructed KPW/GO/PP separator delivered a favorable initial specific capacity (1006 mAh g −1 ) and remarkable cycling performance at 1.0 C (626 mAh g −1 for up to 500 cycles with a decay rate of 0.075% per cycle).