Electrokinetic chromatography (EKC) using micelles of bile salts alone or mixed with sodium dodecyl sulfate (SDS) and neutral, anionic, or cationic cyclodextrins (CDs) in the separation buffer has been employed in order to achieve fast enantiomeric separation of basic drugs. A study of the enantiomeric separation ability of these chiral selectors concerning four basic drugs (epinephrine, terbutaline, clenbuterol, and salbutamol) has been carried out under different experimental conditions. The best chiral selectors to perform the enantiomeric separation of these drugs were neutral beta -CD derivatives, specifically permethylated beta -CD PM-beta -CD. The effect of the PM-beta -CD concentration, temperature, and applied voltage on the enantiomeric resolution of the basic drugs was investigated. The use of a 25 mm ammonium acetate buffer (pH 5.0), 30 mm in PM-beta -CD together with an applied voltage of 20 kV and a temperature of 15 degreesC enabled the individual and fast enantiomeric separation of epinephrine, norepinephrine, terbutaline, clenbuterol, and salbutamol each one into its two enantiomers in less than 3 min. The EKC method was validated (precision and accuracy) to quantitate terbutaline in a pharmaceutical preparation, obtaining a limit of detection of 4 mug/mL.