The last 30 years have seen remarkable changes in interfacial electrochemistry, particularly in the kind of questions that were addressed in electrochemical studies. Ever since classical surface science, traditionally performed under ultrahigh vacuum conditions, has succeeded in describing surfaces and surface reactions on a molecular level, electrochemists longed for a microscopic understanding of the solid/electrolyte interface and, at the same time, searched widely for new experimental ways to reach that goal. Herein, studies are described concerning the structure and the dynamics of bare and adsorbate‐covered electrode surfaces and of metal deposition as a simple, yet important, electrochemical process. In all these cases, the scanning tunneling microscope plays a pivotal role emphasizing the surface‐science approach to the problems.