In addition to high efficiency, short analysis times and small sample volumes, a further attractive feature of capillary electrophoretic techniques is the possibility to achieve, high selectivities. Usually, selectivity control also allows improvement in the resolution. A simple way to enhance the selectivity of capillary electrophoretic separations is to add one or more surfactants above their critical micelle concentration, or in the case of chiral separations to add a chiral selector to the background electrolyte. Because of the dynamic structure of micelles, the aggregation of monomers and size of the micelles can be easily adjusted. This review describes the various type of surfactants used in micellar electrokinetic capillary chromatography, and the chiral selectors employed in enantiomeric separations by capillary electrophoresis. Factors affecting the selectivity are noted. A brief discussion is included of the selectivity enhancement obtainable in non-aqueous media.