Revealing the intrinsic relationships between the structure, properties, and performance of the electrochemical interface is a long-term goal in the electrochemistry and surface science communities because it could facilitate the rational design of electrochemical devices. Achieving this goal requires in situ characterization techniques that provide rich chemical information and high spatial resolution. Electrochemical tip-enhanced Raman spectroscopy (EC-TERS), which provides molecular fingerprint information with nanometer-scale spatial resolution, is a promising technique for achieving this goal. Since the first demonstration of this technique in 2015, EC-TERS has been developed for characterizing various electrochemical processes at the nanoscale and molecular level. Here, we review the development of EC-TERS over the past 5 years. We discuss progress in addressing the technical challenges, including optimizing the EC-TERS setup and solving tip-related issues, and provide experimental guidelines. We also survey the important applications of EC-TERS for probing molecular protonation, molecular adsorption, electrochemical reactions, and photoelectrochemical reactions. Finally, we discuss the opportunities and challenges in the future development of this young technique.

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