A method based on the kinetics stability study on hydrolysis of chlorogenic acid by capillary zone electrophoresis with electrochemical detection (CE-ED) has been developed in this paper. Both cyclic and hydrodynamic voltammograms of chlorogenic acid and its hydrolysis product caffeic acid have been investigated. The conditions for separation of chlorogenic acid and caffeic acid, such as the buffer pH and concentration, the separation voltage, and the injection time have been optimized. Under the optimum CE running conditions, the effects of reaction temperature and pH values of the hydrolysis solutions on the hydrolysis rate constants were further studied. The hydrolysis rate constants of chlorogenic acid were obtained from the concentration change of hydrolysis during the process of hydrolysis. Based on the fact, a simple and economical method for the determination of the hydrolysis rate constant and activation energy of hydrolysis reaction has been developed.