The origin of pseudo peak was studied by means of micellar electrokinetic capillary chromatography with cetyltrimethylaminium bromide as the pseudo stationary phase. It has been pointed that two peaks may appear for one component under certain conditions. Experiments showed that the relative areas of the two peaks of analyte depended on the time and the temperature of reaction between analyte and surfactant, and the concentration of surfactant in the sample solution. It means that the interaction between the analyte and the surfactant is a slow process, and a stable substance can be produced from the interaction. It is the substance and the analyte that may lead to the formation of two peaks. The fast interaction mechanism between the solute and the micellar should be queried from the experiment result. The origin of pseudo peak was studied by means of micellar electrokinetic capillary chromatography with cetyltrimethylaminium bromide as the pseudo stationary phase. Experiments showed that the relative areas of the two peaks of analyte depended on the time and the temperature of reaction between analyte and surfactant, and the concentration of surfactant in the sample solution. It means that the interaction between the analyte and the surfactant is a slow process, and a stable substance can be produced from the interaction. It is the substance and the analyte that may lead to the formation of two peaks. The fast interaction mechanism between the solute and the micellar should be queried from the experiment result.