The adsorption of thiocyanate ions at gold electrodes from an alkaline solution has been studied in situ with IR spectroscopy and surface enhanced Raman spectroscopy (SERS). Mainly S-bound thiocyanate has been observed with SERS even at negative electrode potentials. The spectra show a dependence of the surface-adsorbate vibration on the hydroxide ion concentration in solution. A higher hydroxide ion concentration results in a lower bond strength between the surface and the adsorbed thiocyanate ion. The vibration shifts to higher frequencies at electrode potentials where a gold oxide layer is formed. Different activation procedures employed to confer SERS activity to the electrode surface result in different positions of this vibrational mode. The frequency behavior of the CN-stretching vibration of the adsorbed thiocyanate ion differs from previous results obtained with a neutral electrolyte solution. At more negative electrode potentials the frequency of this mode shows a strong potential dependence, the frequency remains constant at more positive potentials. In addition, at very positive potentials, both the oxidation of thiocyanate to cyanate and the formation of a gold thiocyanate complex have been observed.