The curren troutes to couple dispersive liquid–liquid microextraction (DLLME) with capillary electrophoresis (CE) are evaporation of water immiscible extractants and backextraction of analytes. The former is not applicable to extractants with high boiling points,the latter being effective only for acidic or basic analytes, both of which limit the further application of DLLME-CE. Inthisstudy, with 1-octanol as a model DLLME extractant and six phenols as model analytes, a novel method based on acetonitrile stacking and sweeping is proposed to accomplish large-volume injection of 1-octanol diluted with a solvent–saline mixture before micellar electrokinetic chromatography. Brij-35 and B-cyclodextrin were employed as pseudostationary phases for sweeping and also for improving the compatibility of sample zone and aqueous running buffer. A short solvent–saline plug was used to offset the adverse effect of the water immiscible extractrantion focusing efficiency. The key parameters affecting separation and concentration were systematically optimized;