The separation of carboxylic enantiomers in the pharmaceutical field using high-performance liquid chromatographic and capillary electrophoretic techniques is reviewed. The techniques used for chiral separation include diastereomer derivatization, a chiral mobile phase, a chiral stationary phase (high-performance liquid chromatography) and chiral additives (capillary electrophoresis). Practical and conventional separation systems for pharmaceutical applications, such as pharmacokinetics, optical purity testing and stability studies, are described. A comprehensive collection of applications to carboxylic drugs and other carboxylic compounds of pharmaceutical interest is listed in the tables. The characteristics of each enantioseparation method are also discussed briefly.