Lithium–sulfur (Li-S) batteries offer a high theoretical energy density but suffer from poor cycling stability and polysulfide shuttling, which limits their practical application. To address these challenges, we developed a PANI-modified MoS₂-NG composite, where MoS₂ nanoflowers were uniformly grown on graphene oxide (GO) through PANI modification, resulting in an increased interlayer spacing of MoS₂. This expanded spacing exposed more active sites, enhancing polysulfide adsorption and catalytic conversion. The composite was used to prepare MoS₂-NG/PP separators for Li-S batteries, which achieved a high specific capacity of 714 mAh g⁻¹ at a 3 C rate and maintained a low capacity decay rate of 0.085% per cycle after 500 cycles at 0.5 C. The larger MoS₂ interlayer spacing was key to improving redox reaction kinetics and suppressing the shuttle effect, making the MoS₂-NG composite a promising material for enhancing the performance and stability of Li-S batteries.