Exocytosis, the fusion of intracellular vesicles with the membrane and subsequent release of vesicular contents, is important in intercellular communication. The release event is a rapid process (milliseconds), hence detection of released chemicals requires a detection scheme that is both sensitive and has rapid temporal dynamics. Electrochemistry at carbon-fiber microelectrodes allows time-resolved exocytosis of electroactive catecholamines to be observed at very low levels. When coupled with constant-potential amperometry, the number of molecules released and the kinetics of quantal release can be determined. The rapid response time (milliseconds) of microelectrodes makes them well suited for monitoring the dynamic process of exocytosis.