The commercialization of Lithium-sulfur batteries was limited by the polysulfide shuttle effect, and modifying the routine separator was an effective method to solve this problem. In this work, a novel hierarchically porous polypyrrole sphere (PPS) was successfully prepared by using silica as hard-templates. As-prepared PPS was slurry-coated on the separator, which could reduce the polarization phenomenon of the sulfur cathode, and efficiently immobilize polysulfides. As expected, high sulfur utilization was achieved by suppressing the shuttle effect. When tested in the lithium-sulfur battery, it exhibited a high capacity of 855 mAh·g-1 after 100 cycles at 0.2 C, and delivered a reversible capacity of 507 mAh·g-1 at 3 C, showing excellent electrochemical performance.