The　practical　application　of　lithium–sulfur　batteries　has　been　limited　by　the　detrimental　shuttling　behavior　and　sluggish　conversion　kinetics　of　lithium　polysulfides　(LiPSs),　especially　under　high　sulfur　loading　and　lean　electrolyte　dosage.　Although　experimental　and　theoretical　studies　show　that　introducing　defect　and　Fe–N4　site　in　carbon　materials　is　the　desirable　strategy　to　expedite　LiPSs　conversion,　the　synergetic　effect　between　them　for　sulfur　redox　chemistry　is　hardly　explored.　Herein,　derived　from　a　well-define　Fe–N4　macrocyclic　pristine　iron　phthalocyanine　molecules　(FePc)　coordinated　on　the　defective　carbon　nanosheets　(FePc-DC),　the　marriage　and　synergetic　effect　between　defective　carbon　and　FePc　molecules　can　induce　remarkable　Fe　center　electron　delocalization　and　regulate　the　local　electron　redistribution　between　FePc-DC　interfaces,　thus　brings　improved　LiPSs　adsorption　ability　and　conversion　reaction　rate.　Meanwhile,　the　robust　two-dimensional　flake　texture　with　large　surface　area　and　abundant　porosity　ensures　robust　physical　confinement　and　fast　electron/ion　transfer.　Attributed　to　such　unique　features,　the　lithium–sulfur　batteries　with　FePc-DC　cathode　delivers　good　electrochemical　performance　with　high　areal　capacity　of　5.53　mAh/cm2　under　high　sulfur　mass　loading　of　4.9　mg/cm2　and　low　electrolyte/sulfur　ratio　of　6.5　μL/mg,　demonstrating　great　potential　in　advanced　Li–S　batteries.　©　2022　Elsevier　Ltd