In this study, a capillary electrophoresis method was developed for the determination of cationic surfactants, benzethonium and cetylpyridinium ions, which are commonly used as preservatives in various pharmaceutical and cosmetic products. Determination was performed in a fused-silica capillary using a mixed 75 mmol/L phosphoric acid and 50% acetonitrile electrolyte at pH 2.5. Analysis of benzethonium and cetylpyridinium ions was achieved in around 5 min. Repeatability in migration times (R.S.D.%) for benzethonium and cetylpyridinium ions were 0.3. The calibration curves were linear from 0.0125 to 0.400 mmol/L for benzethonium ions and from 0.025 to 0.400 mmol/L for cetylpyridinium ions. The minimum detection limits (signal-to-noise ratio = 3) are 1.47 and 4.30 μ g/mL for benzethonium and cetylpyridinium ions, respectively. The method was applied to the analysis of benzethonium ion in a cosmetic product and cetylpyridinium ion in a mouthwash. © 2004 Elsevier B.V. All rights reserved.