Raman vibrational bands from surface and solution species formed during potential cycles at gold electrodes in chloride and cyanide solutions were examined using surface-enhanced Raman scattering (SERS) spectroscopy. In acidic or neutral solution, chloride ion is adsorbed prior to gold dissolution and v(AuCl)-(ads) ads Stark-shifts to higher wavenumbers with increasing electrode potential, but the SERS intensity of this band is significantly diminished when leaching commences. In cyanide solutions, the presence of specifically adsorbed cyanide ions at the electrode surface at the lower potential limit was indicated by Stark-shifted Raman bands characteristic of carbon-nitrogen stretching. Bond formation between cyanide and gold, evidenced by vibrational modes due to gold-carbon stretching and gold-carbon-nitrogen bending, commenced near the potential at which voltammetric currents consistent with gold dissolution were observed. At high potentials, cyanide was displaced from the surface and a Raman band characteristic of gold-oxygen stretching appeared. Oxidation of cyanide to cyanate was also indicated in this region by a Raman band characteristic of the carbon-nitrogen stretch of the cyanate ion. The voltammetric current was depressed when gold oxide was formed on the surface. Reductive removal of the oxide layer on the reverse sweep was followed by facile gold dissolution and accompanied by a rapid coverage of cyanide species. © 2005 The Electrochemical Society. All rights reserved.