Thecurrentroutestocoupledispersiveliqui–liquidmicroextraction(DLLME)withcapillaryelec-trophoresis(CE)areevaporationofwaterimmiscibleextractantsandbackextractionofanalytes.Theformerisnotapplicabletoextractantswithhighboilingpoints,thelatterbeingeffectiveonlyforacidicorbasicanalytes,bothofwhichlimitthefurtherapplicationofDLLME-CE.Inthisstudy,with1-octanolasamodelDLLMEextractantandsixphenolsasmodelanalytes,anovelmethodbasedonacetonitrilestackingandsweepingisproposedtoaccomplishlarge-volumeinjectionof1-octanoldilutedwithasolvent–salinemixturebeforemicellarelectrokineticchromatography.Brij-35and-cyclodextrinwereemployedaspseudostationaryphasesforsweepingandalsoforimprovingthecompatibilityofsam-plezoneandaqueousrunningbuffer.Ashortsolvent–salineplugwasusedtooffsettheadverseeffectofthewaterimmiscibleextractantonfocusingefficiency.Thekeyparametersaffectingseparationandconcentrationweresystematicallyoptimized;