Electrocatalysis and electrosynthesis, which convert the electrical energy and store them in the chemical forms, have been considered as promising technologies to utilize green renewable energy sources. Most of the studies focused on developing novel active molecules or advanced electrodes to improve the performance. However, the direct acquisition and electron transferring will be limited by the intrinsic characters of the electrodes. The introduce of redox media-tors, which are served as the intermediate electron carriers or reservoirs without changing the final products, provide a unique approach to accelerate the electrochemical performance of these energy conversions. This review provides an overview of the recent development of electrocatalysis and electrosynthesis by using redox mediators, and provides a comprehensive discussion toward focusing on the principles and construction of these systems.