Microelectrode arrays-based double electrode systems possess the property of diffusion layer overlapping between the two sets of electrodes. They have received increased attention in recent years in the field of electrochemistry and electroanalytical chemistry. This review introduces the fabrication, characterization, and applications of microelectrode arrays-based double electrode systems. The progress of photolithography enables and benefits microfabrication of the electrode systems with various geometries. As an essential step before electrochemical applications, various characterization methods are addressed to monitor the quality of the fabricated electrodes. Following that, applications as electrochemical sensors in generator-collector mode are discussed. Then, electrochemical sensors in bipolar mode, an interesting phenomenon existing in double electrode systems, are also introduced. Finally, applications of double electrode systems to the measurement of fundamentally electrochemical parameters are demonstrated.