One of the most important tasks in physical electrochemistry today is the determination, on a microscopic level, of the structure and the properties of the solid–electrolyte interface. To obtain such information, two somewhat different approaches are currently employed. The first one deals with in situ spectroscopy, i.e., with spectroscopic techniques which are applicable in the presence of the electrolyte. The second route involves electrode emersion and the study of the surface properties outside the electrochemical cell, e.g., under UHV conditions. In the following, selected examples for the study of electrode surfaces are given, which are believed to be of topical interest to a general surface science audience. Those include surface states at the metal–electrolyte interface, adsorbate-induced surface reconstruction and restructuring, and the study of metal deposits in the submonolayer range.