The adsorption of 4-dimethylamino-4′-nitrostilbene (DANS) on polycrystalline silver and gold electrodes from neutral and acidic electrolyte solutions saturated with DANS was studied using cyclic voltammetry and surface-enhanced Raman (SER) spectroscopy. With both electrode metals a tilted or perpendicular orientation of the adsorbed molecule with an interaction via the nitro group is postulated, based on SER spectra recorded at various electrode potentials within a range where only adsorption occurs. The adsorption does not influence the vibrational modes of DANS significantly, which makes further adsorptive interaction via other binding sites of the molecule unlikely.