The development, optimization and application of a chiral CE (capillary electrophoresis) method for the determination of the enantiomer content of a new cholesterol-lowering drug (BMS-180431-09) is discussed. The chiral CE technique, cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC), was employed with hydroxypropyl β-cyclodextrin as the chiral selector in the run buffer. The detection limit of the unwanted enantiomer was about 0.06% w/w. The effect of various parameters on the separation, validation data and examples of the application of the chiral CE method are included.