Ultrasound-assisted emulsification microextraction and dispersive liquidliquid microextraction were compared for extraction of ephedrine, norephedrine, and pseudoephedrine from human urine samples prior to their determination by capillary electrophoresis. Formation of a microemulsion of the organic extract with an aqueous solution (at pH 3.2) containing 10% methanol facilitated the direct injection of the final extract into the capillary. Influential parameters affecting extraction efficiency were systematically studied and optimized. In order to enhance the sensitivity further, field-amplified sample injection was applied. Under optimum extraction and stacking conditions, enrichment factors of up to 140 and 1750 as compared to conventional capillary zone electrophoresis were obtained resulting in limits of detection of 1233 mu g/L and 1.02.8 mu g/L with dispersive liquidliquid microextraction and ultrasound-assisted emulsification microextraction when combined with field-amplified sample injection. Calibration graphs showed good linearity for urine samples by both methods with coefficients of determination higher than 0.9973 and percent relative standard deviations of the analyses in the range of 3.48.2% for (n = 5). The results showed that the use of ultrasound to assist microextraction provided higher extraction efficiencies than disperser solvents, regarding the hydrophilic nature of the investigated analytes.