3,4-ethylenedioxythiophene　(EDOT)　unit　featuring　electron　donor　and　self-structuring　properties,　has　been　considered　as　the　conducting　polymers　resources　for　organic　electronic　devices.　However,　construction　of　covalent　organic　frameworks　(COFs)　with　EDOT　building　blocks　has　not　been　reported.　Herein,　a　novel　conductive　EDOT-based　COF　(EDOT-Por-COF)　with　enhanced　chemical　interaction　and　conductivity　was　synthesized　as　the　electrocatalysts　accelerating　the　conversion　kinetics　of　soluble　polysulfides.　The　corresponding　EDOT-Por-COF　with　electron-rich　conjugated　microenvironment　generates　higher　sulfur　affinity　and　polysulfides　catalytic　activity,　which　is　further　verified　by　experimental　data　and　density　functional　theory　(DFT)　calculations.　The　introduction　of　an　electron-rich　surrounding　environment　alleviates　the　tendency　of　charge　loss　at　Co　sites　and　guarantees　an　optimized　electronic　structure　around　the　Co　sites,　thus　improving　the　adsorption　strength　and　electron　transfer　between　the　Co　sites　and　polysulfides,　contributing　to　an　improved　catalytic　capability　on　polysulfides.　As　a　result,　the　assembled　cell　displays　a　ultrahigh　discharge　capacity　of　1585.9　mAh　g−1　at　0.1　C,　a　low　the　capacity　decay　rate　of　0.031　%　per　cycle　for　2000　cycles　at　1　C　and　a　high　rate　capacity　of　763.9　mAh　g−1　at　5　C.　This　work　supports　a　new　insight　into　electrocatalyst　structural　regulation　to　boost　the　electrochemical　performance　of　Li–S　batteries.　©　2024　Elsevier　Ltd