Two separation methods were developed for the determination of S- and R-perindopril tert-butylamine (erbumine salt) (PER): high performance liquid chromatography (HPLC) and capillary electrophoresis (CE). The HPLC method uses a chiral stationary phase (CSP), ChiraDex column constituting -cyclodextrin chemically bonded to spherical silica gel particles. The mobile phase consisted of phosphate buffer (50 mM, pH 3.0) and acetonitrile (45 : 55 v/v). The flow rate was 1.0 mL min1 and the detection wavelength was 210 nm. In CE, 2-hydroxylpropyl--cyclodextrin (10 mM) was used as a chiral selector. It was added to the background buffer composed of phosphate buffer (100 mM, pH 7.0) and methanol (15% v/v). The applied voltage was 15 kV and the detection was carried out using a diode array detector. All factors affecting the chromatographic or electrophoretic separations were studied and optimized. The linear concentrations ranged from 5–150 and 25–800 µg mL1 with detection limits of 2.3 and 14.7 µg mL1 for HPLC and CE methods, respectively. The methods were validated according to ICH and USP guidelines. The suggested methods were applied for the determination of S-PER in bulk powder and commercial tablets containing PER erbumine racemate.