Adsorption of Li2S x on pristine and defective (Stone-Wales (SW) and vacancy) graphene is studied using density functional theory. Results show that the interaction between Li2S x and graphene is dominated by dispersion interaction (physisorption), which depends on the size of molecule as well as the existence and type of defect sites on graphene. We find that single Li2S x molecules interact only slightly stronger to the SW sites than to the defect-free sites, but they interact very strongly with single-vacant defects. In the later cases, the vacant site catches one S atom from the Li2S x molecule, leading to the formation of a Li2S x−1 molecule, which adsorbs weakly on the created S-doped graphene. This study suggests that defect sites can not improve the ability of graphene to catch lithium polysulfides in Li-S batteries.