A powerful capillary electrophoresis (CE) method, with preconcentration in excess of 100,000-fold, has been developed by using a specific characteristic of perfluoro surfactants. Highly sensitive determination and separation of polycyclic aromatic hydrocarbons (PAH) were achieved by following a combination of two kinds of efficient preconcentration method using perfluoro surfactants. The two preconcentration methods combined were homogeneous liquid-liquid extraction for off-line concentration and a sweeping method as on-line concentration. Five PAH (1,2,3,4-dibenzanthracene, 1,2,5,6-dibenzanthracene, benzo( a)pyrene, benzo( e)pyrene, and pyrene) were investigated, and were completely separated. When the concentration-factor (volume ratio) was 8335-fold, the determination limits were in the range 10(-10) to 10(-9) mol L(-1). The maximum concentration-factor (volume ratio) obtained was 125,000-fold. Addition and recovery experiments were performed for three kinds of natural water (rain water, river water, and spring water).