Recycling　of　valuable　solutes　and　recovery　of　organic　solvents　via　organic　solvent　nanofiltration　(OSN)　are　important　for　sustainable　development.　However,　the　trade-off　between　solvent　permeability　and　solute　rejection　hampers　the　application　of　OSN　membranes.　To　address　this　issue,　the　poly(3,4-ethylenedioxythiophene):poly(styrene　sulfonate)　(PEDOT:PSS)　nanoparticle　membrane　with　hierarchical　pores　is　constructed　for　OSN　via　vacuum　filtration.　The　small　pores　(the　free　volume　of　the　polymer　chain)　charge　for　the　solute　rejection　(high　rejection　efficiency　for　low　molecule　weight　solute)　and　allow　solvent　passing　while　the　large　pores　(the　void　between　two　PEDOT:PSS　nanoparticles)　promote　the　solvent　transport.　Owing　to　the　lack　of　connectivity　among　the　large　pores,　the　fabricated　PEDOT:PSS　nanoparticle　membrane　enhanced　solvent　permeance　while　maintaining　a　high　solute　rejection　efficiency.　The　optimized　PEDOT:PSS　membrane　affords　a　MeOH　permeance　of　7.2　L　m(-2)　h(-1)　bar(-1)　with　over　90%　rejection　of　organic　dyes,　food　additives,　and　photocatalysts.　Moreover,　the　rigidity　of　PEDOT　endows　the　membrane　with　distinctive　stability　under　high-pressure　conditions.　The　membrane　is　used　to　recycle　the　valuable　catalysts　in　a　methanol　solution　for　150　h,　maintaining　good　separation　performance.　Considering　its　high　separation　performance　and　stability,　the　proposed　PEDOT:PSS　membrane　has　great　potential　for　industrial　applications.