Rare earth elements and graphene composites exhibit better catalytic properties in energy storage materials. The introduction of rare earth oxide and graphene composites as functional layers into the separator to seal the "shuttle effect" formed by polysulfides during the discharge process has proven to be effective. In this study, we prepared CeO2/graphene composites (labeled as CeG) by intercalation exfoliation and in situ electrodeposition methods simultaneously, in which CeO2 was encapsulated in large folds of graphene, which exhibited good defect levels (ID/IG < 1) and its intrinsically superior physical structure acted as a shielding layer to hinder the shuttle of polysulfides, improving the cycling stability and rate of cell performance. The separator cell with CeG achieves an initial discharge specific capacity of 1133.5 mAh/g at 0.5C, excellent rate performance (978.5 mAh/g at 2C), and long cycling (790 mAh/g after 400 cycles).