A rapid and simple method for separation of enantiomers of a variety of compounds is desirable as information regarding the enantiomeric composition may not be provided by the chemical suppliers especially chemical drug compounds. These drugs are commercially available with no information regarding whether they are pure enantiomers or racemic mixtures. Each enantiomer may have different pharmacological activity. Thus the information of chirality is important. This work aims to employ a capillary electrophoresis with UV detection as a simple and rapid method for separation of enantiomers to determine the compound chirality. The developed method has been applied for separation of different functional chemicals of drugs, such as β-blockers and neurotransmitter, by using a single capillary electrophoresis method. The buffer conditions for the capillary method were optimized with regards to the chiral selector type and concentration for improving the efficiency of enantiomer separation. The optimum condition of buffer was phosphate buffer (20.0 mM, pH 2.7) containing CM-β-CD (4.0 mM). The single method was applied to the separation of four different drug compounds, viz. atenolol, propranolol, octopamine, and ibuprofen, to demonstrate the effectiveness of the developed method