Pharmaceuticals in human plasma are determined on underivatized fused-silica capillaries by micellar electrokinetic capillary chromatography (MEKC) without sample pretreatment. Our best method to date uses as running buffer a sodium dodecyl sulfate (SDS) containing borate buffer (60 mM with 200 mM SDS) at pH 10. Between runs, proteins adsorbed to the capillary wall are removed by an acetonitrile and SDS-buffer rinsing regimen (50% v/v each). A day-to-day precision for relative peak areas of about 2% relative standard deviation (RSD; n > 40) has been reached. Different rinsing approaches are discussed (salts, enzyme-containing solutions, organic solvents, hydrofluoric acid). The separation system is tested in a concentration range between approximately 100 mg/L-10 mg/L. Correlations between the limit of quantitation, the limit of detection and the signal/noise are discussed. The applicability of the system is demonstrated for the pharmaceuticals acetaminophen, salicylic acid, sulfamethoxazole, tolbutamide, and trimethoprim.