Examples of several classes of cardiovascular drugs have been separated using capillary electrophoresis and its associated application, micellar electrokinetic chromatography. The therapeutic classes of drag investigated include beta-blockers, antiarrhythmic, calcium channel antagonists and angiotensin converting enzyme inhibitors. The exceptional selectivity of capillary electrophoresis is demonstrated using conditions that separate some twenty cardiovascular drugs in a single mixture, including all the aforementioned classes of drugs. The compounds have unrelated structures and varying molecular masses and yet are still resolved using a single set of conditions. The application of such selectivity is discussed together with a comparison with high-performance liquid chromatography.