Despite their high theoretical capacity density (1675 mAh g(-1)), the application of Li S batteries has been seriously hindered by the shuttle effect of polysulfides. Here, inspired by the working principle of natural spider webs, we synthesized a spider-web-like nanocomposite in which many hollow mesoporous silica (mSiO(2)) nanospheres/Co nanoparticles were threaded by interconnected nitrogen-doped carbon nanotubes (NCNTs). Then the nanocomposite (denoted as Co/mSiO(2) NCNTs) was coated on the commercial separator by a simple infiltration to mitigate the above issue. The intimate combination of three-dimensional conductive networks (NCNTs) with abundant polysulfide adsorbent sites (SiO2 and N)/polysulfide conversion catalysts (Co and Co N species) allows the Co/mSiO(2) NCNTs coating layer to not only effectively capture polysulfides via both physical confinement and chemical bonding but also accelerate the redox kinetics of polysulfides significantly. Furthermore, the combination of ex situ experiment and theoretical calculation demonstrates that the reversible adsorption/desorption of polysulfides on mSiO(2) nanospheres benefits uniform deposition of Li2S2/Li2S on the conductive networks, which contributes to long-term cycling stability. As a result, Li S batteries with Co/mSiO(2) NCNTs-coated separators exhibited both excellent cycling stability and rate performance.