Thiocyanate (SCN) adsorption on an Au electrode is examined using surface-enhanced Raman scattering (SERS) measurements, along with detailed density functional theory (DFT) calculations'. Both the calculation and the spectroscopic measurements show that three different geometries are adopted by SCN adsorption in the potential region studied (0.0 V less than or equal to E less than or equal to 1.2 V vs NHE). At low potential both N-bound and S-bound forms are found, at intermediate potentials around the potential of zero charge (E-pzc) the S-bound form dominates, and at high potentials SCN associates with the Au surface via a bridging geometry. The Stark slope observed for the C-N stretch in the N- and S-bound forms is positive, while the bridge form exhibits a negative Stark slope. DFT calculations show that the potential-dependent reorientation of SCN arises from overlap of specific SCN-based orbitals with the Fermi level of the Au surface; as the Fermi energy changes, different orbital overlaps are found. The calculations also provide an explanation for the different signs of the Stark slope observed for different geometries. For the end-on adsorption, the lowest unoccupied molecular orbital (LUMO) associated with the C-N bond is antibonding, while the corresponding LUMO in the bridge form is bonding.