Unraveling the mechanistic details of neurotransmitter exocytosis is arguably among the most important molecular problems in neuroscience today. Investigations at single cells, particularly with electrochemical methods, have given unique chemical and biological insight into this process at the fundamental level. The rapid response time (submillisecond) of microelectrodes makes them well suited for monitoring the dynamic process of exocytosis. We review here recent developments in electrochemical techniques to spatially and simultaneously detect exocytosis across a single cell and to measure the transmitter content of single vesicles removed from cells. The former method is used to demonstrate dynamic heterogeneity in release across a cell, and in the latter work comparison is made between vesicle content and release to conclude that only a fraction of the transmitter is released during full exocytosis.