A sensitive and rapid method was developed for angiotensin-converting enzyme (ACE) activity determination by micellar electrokinetic capillary chromatography (MECC). MECC was carried out to separate and quantify the products of the enzymatic reacting using Hip-Leu-His as the substrate in 20 mmol/L boric acid-borate buffer (pH 9.0) including 50 mmol/L SDS as the run buffer at an applied voltage of 8.1 kV. The electrophoresis was monitored at 228 nm, and completed in 6 minutes. The detection limits of ACE activity was 5 pmol/min(signal to noise ratio was 2).