The polymerized surfactant poly(sodium N-undecylenyl amino L-valinate) [poly(L-SUV)] has been used in micellar electrokinetic capillary chromatography for the chiral separation of various acidic and basic drugs, as well as neutral compounds. Under the conditions studied, poly(L-SUV) was shown to be a very versatile anionic chiral selector in the pH range of 5.6-11. The micelle was used for the enantioseparation of coumarinic anticoagulant drugs with various buffers under moderately acidic conditions. Neutral and alkaline buffer conditions were used to successfully separate the neutral atropisomers (+/-)-1,1'-bi-2-naphthol, (+/-)-1,1'-binaphthyl-2,2'-diamine, and Tröger's base. Chiral separation of the cationic paveroline drugs, laudanosine, norlaudanosoline, and laudanosoline, was influenced by pH and the use of coated capillaries. The acquired data focused on optimizing the migration times, capacity and separation factors, and electrophoretic mobilities of the various racemic mixtures.