<p>In the mid-1970s, surface-enhanced Raman spectroscopy (SERS) was discovered on an electrochemically roughened silver electrode surface, marking a milestone in the field of surface/interface analysis. Electrochemical SERS (EC-SERS), the initial application of SERS, has evolved into a powerful technique for acquiring fingerprint vibrational information from the interfaces and interphases in electrochemical systems, driven by advancements in nanoscience and nanotechnology, hence becoming one of the most significant spectroelectrochemical techniques for investigating electrochemical energy. However, achieving a groundbreaking discovery and subsequently establishing a new research field was a challenging and arduous endeavor. Therefore, it is essential to review the development of EC-SERS and its family members, including electrochemical tip-enhanced Raman spectroscopy (EC-TERS) and electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) over the past five decades. This review begins with the discovery of SERS in the mid-1970s, followed by the explosive growth driven by nanoscience and then the development of <i>operando</i> spectroelectrochemistry. Furthermore, the recent applications of <i>in situ/operando</i> studies in electrochemical energy storage and conversion, as well as investigations of corrosion inhibitors, electroplating, and electrodeposition, are discussed. Finally, a perspective on the new research paradigms, including emerging <i>operando</i> spectroelectrochemistry and artificial intelligence (AI)-nano-driven technologies for EC-SERS, is presented.</p>