This chapter reviews the theory and methodological developments of on-line concentration techniques for the determination of environmental pollutant samples, such as organic and inorganic compounds in capillary zone electrophoresis (CZE) and also in micellar electrokinetic chromatography (MEKC). Topics covered include a variety of on-line preconcentration strategies, which are now generally referred to as sample stacking and sweeping techniques. For each technique, surveyed methods are tabulated in order to assist in method selection. Innovative applications of sample stacking and sweeping to advanced environmental research are also emphasized. In addition, other comparative on-line concentration methods for environmental samples, namely, isotachophoretic stacking and anion and cation selective exhaustive injection-sweeping are briefly discussed.