This paper reports a strategy to couple liquid-liquid semimicroextraction (LLsME) with capillary electrophoresis (CE) based on a newly introduced on-column decomposable sample matrix, ethyl acetate (EA). LLsME was performed in volumetric flasks of 100 mL. Samples containing an aqueous phase were first saturated with EA. Then, an extra 500 mu L of EA was added to extract the samples. Sample injection in CE could be made in hydrodynamic mode by dipping the injection end of the capillary into the organic (EA) phase in the volumetric flasks. As a demonstration, alkylphenones in water samples were extracted by LLsME into EA and subjected to separation by micellar electrokinetic chromatography (MEKC). Alkylphenones of C8-C12 with concentrations of about 10 ppb can be concentrated and detected after extraction; extraction efficiencies range from 72- to 334-fold. Linearity of extraction was determined and the effect on reproducibility by spiking an internal standard was studied. The method developed is time-saving and requires no further special experimental device other than a basic CE setup. Therefore, it would be readily acceptable for routine analysis, especially in analytical laboratories dealing with environmental samples.