Lithium‐sulfur (Li‐S) batteries display promise as redox‐based batteries, where separators are an essential part of preventing short‐circuiting of the positive and negative electrodes, while the shuttle effect is a critical issue of separators. Currently, commercial PP separators are weak in inhibiting the polysulfides shuttling, so modified separators are needed to inhibit it to improve the battery performance. This paper reports that CeVO4/KB composites act as separator materials. CeVO4/KB modified PP separators enhanced the adsorption of LiPSs, accelerated the rate of Li+ migration, and catalyzed the conversion of LiPSs. These bring about the effect that CeVO4/KB/PP batteries reach 1200.9 mAh g‐1 in the first cycle with a capacity retention rate of 86.5% after 100 cycles at 0.2 C and reach 882.7 mAh g‐1 of the initial cycle with a capacity decay rate of 0.063% after 1000 cycles at 3 C. This work introduces rare earth metal vanadates to modify the separator, adding new ideas for designing separators for good‐performance batteries.