It　is　well-known　that,　under　lean　electrolyte　and　high　sulfur　loading　conditions,　it　is　challenging　to　achieve　a　high　discharge　platform,　discharge　capacity,　and　cycling　stability　for　lithium-sulfur　(Li-S)　batteries.　Here　we　report　a　free-standing　sulfur　cathode　that　can　efficiently　adsorb　and　electrochemically　catalyze　polysulfides.　A　cationic　polymer,　polyquaternium-10　(P10),　is　adopted　as　a　new　binder　that　produces　viscoelastic　fibers　during　casting,　facilitates　lithium-ion　transportation,　and　electrostatically　regulates　polysulfides.　The　cationic　polymer　promotes　the　formation　of　the　free-standing　cathode　with　a　desirable　web-like　microstructure.　The　Li-S　battery　constructed　by　the　free-standing　cathode　with　sulfur　mass　loading　of　6　mg　cm-2　achieves　a　high　initial　areal　capacity　of　7.09　mAh　cm-2　(i.e.,　344.5　Wh　kg-1　and　471.6　Wh　l-1)　and　stable　areal　capacity　of　4.48　mAh　cm-2　(i.e.,　217.6　Wh　kg-1　and　235.8　Wh　l-1)　during　cycling　at　a　low　electrolyte/sulfur　ratio　of　4　μL　mg-1　©　2022　American　Chemical　Society.