Enantiomers of five racemic β2-agonists were investigated by capillary electrophoresis employing a hydroxypropyl-β-cyclodextrin (HP-β-CD). The effects of the concentration of HP-β-CD added to the background electrolyte and of the pH of the buffer on the effective mobility and resolution of the studied compounds were examined. Very good resolution was achieved for terbutaline and clenbuterol; salbutamol and bambuterol was able to be partially resolved. Enantioselectivity and resolution were influenced by the concentration of the HP-β-CD, buffer composition and pH.