Capillary electrochromatography (CEC) with octadecyl-silica-packed capillary columns was evaluated in the separation of nonpolar compounds, e.g., pyrethroid insecticides, using surfactant-rich mobile phases. This novel concept is referred to as surfactant-mediated capillary electrochromatography (SM-CEC), and is based on including a charged surfactant, namely sodium di-2-ethylhexyl sulfosuccinate (DOSS), in the mobile phase. Under these conditions, DOSS plays the role of a slowly moving pseudostationary phase so that solutes are partitioned between a mobile phase, a fixed stationary phase and a slowly moving pseudostationary phase. The SM-CEC system was investigated with pyrethroid insecticides over a wide range of DOSS and acetonitrile concentrations in the mobile phase. Pyrethroid insecticides, which are very hydrophobic solutes consisting of geometric isomers and diastereomers, were better resolved in SM-CEC than in straight CEC.