It has been known for some time that the group lb metals, copper, silver, and gold, are unique with regard to the magnitude of the surface-enhanced Raman spectroscopy response recorded, especially for organic bases, at the metal/solution interface. Another unique feature of these three metal electrode systems is described here; they display an adatom (M*)/hydrous oxide transition in which the cation is in the univalent (M+) state. It is suggested that these are the only metals known to date that readily yield relatively insoluble, surface-bound, univalent hydrous oxide species that behave as strong bases. The redox transition in question, M*/M(1) hydrous oxide, displays an unusual shift in potential upon altering the solution pH; this shift (previously reported for gold and silver) was monitored in the present work by recording the change in onset (anodic sweep)/termination (cathodic sweep) potential for dimethylamine borane oxidation, a reaction induced by the oxidized form of the couple acting as a mediator. It was pointed out that the two unique features of these three metals have the same basis, i.e., an array of univalent cations attached to the electrode surface. © 1990, The Electrochemical Society, Inc. All rights reserved.