Communication between cells by release of specific chemical messengers via exocytosis plays crucial roles in biological process. Electrochemical detection based on ultramicroelectrodes (UMEs) has become one of the most powerful techniques in real-time monitoring of an extremely small number of released molecules during very short time scales, owing to its intrinsic advantages such as fast response, excellent sensitivity, and high spatiotemporal resolution. Great successes have been achieved in the use of UME methods to obtain quantitative and kinetic information about released chemical messengers and to reveal the molecular mechanism in vesicular exocytosis. In this paper, we review recent developments in monitoring exocytosis by use of UMEs-electrochemical-based techniques including electrochemical detection using micrometer and nanometer-sized sensors, scanning electrochemical microscopy (SECM), and UMEs implemented in lab-on-a-chip (LOC) microsystems. These advances are of great significance in obtaining a better understanding of vesicular exocytosis and chemical communications between cells, and will facilitate developments in many fields, including analytical chemistry, biological science, and medicine. Furthermore, future developments in electrochemical probing of exocytosis are also proposed.