Enantiomeric separation of epinephrine and salbutamol was investigated by micellar electrokinetic chromatography employing β-cyclodextrin as chiral additive in ammonium chloride-ammonia solution. The analytes were detected by electrochemistry using gold microelectrode at +0.65 V versus SCE reference electrode. The effects of detection potential,concentration of β-cyclodextrin, concentration of sodium dodecyl sulfate, pH value of electrolyte and applied voltage were discussed.