The formation origin of two peaks in micellar electrokinetic capillary chromatography by using cetyltrimethylaminium bromide (or sodium dodecyl sulfate) as pseudo stationary phase is studied. It is pointed out that two peaks may appear for one component in certain conditions. Experiments show that the relative areas of the two peaks of the corresponding component depend on the time and temperature of reaction between the analyte and the surfactant, and thconcentration of surfactant in the sample solution. One of the two peaks increase with the increase of surfactant concentration in the sample solution while reverse for another peak. Temperature can accelerate the reaction process. This means that the interaction between analyte and surfactant is a slow process, and a stable substance can be produced from the interaction and leads to the formation of two peaks. The standpoint is confirmed by the infrared and nuclear magneticresonance spectra of the product from the reaction between cetyltrimethylaminium bromide and m-hydroxyl benzoic acid. The formation origin of two peaks in micellar electrokinetic capillary chromatography by using cetyltrimethylaminium bromide (or sodium dodecyl sulfate) as pseudo stationary phase is studied. It is pointed out that two peaks may appear for one component in certain conditions. Experiments show that the relative areas of the two peaks of the corresponding component depend on the time and temperature of reaction between the analyte and the surfactant, and thconcentration of surfactant in the sample solution. One of the two peaks increase with the increase of surfactant concentration in the sample solution while reverse This means that the interaction between analyte and surfactant is a slow process, and a stable substance can be produced from the interaction and leads to the formation of two peaks. The standpoint is confirmed by the infrared and nuclear magneticresonance spectra of the product from the reaction between cet yltrimethylaminium bromide and m-hydroxyl benzoic acid.