Single drop microextraction (SDME) is a convenient and powerful preconcentration method for CE before injection. By simple combination of sample-handling sequences without modification of the CE apparatus, a drop of an aqueous acceptor phase covered with a thin organic layer was formed at the tip of a capillary; 10 min SDME of fluorescein and 6-carboxyfluorescein from a donor phase of pH 1 to an acceptor phase of pH 9 provided 110-fold enrichments without stirring the donor phase. To improve the concentration effect further, SDME was coupled with an on-line (after injection) sample preconcentration method, sweeping, in which analytes in a long sample zone are accumulated at the boundary of a pseudostationary phase penetrating into the sample zone. It is thus necessary to inject a sample of much larger volume than that of a drop in typical SDME. A Teflon sleeve over the capillary inlet allowed a large volume drop to be held stably during extraction. By in-line coupling 10 min SDME and sweeping of a 30 nL sample using a cationic surfactant dodecyltrimethylammonium, enrichment factors of the double preconcentration were increased up to 32000.