Surface-enhanced Raman spectra of benzene were observed from a silver electrode in aqueous solutions. SERS of benzene showed remarkable potential dependence and also anion-induced spectral changes. A pair of ring breathing bands appeared at 984 and 992 cm −1, which suggested that there are at least two types of adsorbed benzene on the electrode surfaces. These are ascribed to the species located on anion-free adatom sites and on the specifically adsorbed anions, respectively. Time-resolved SERS was investigated in order to confirm these assignments of the adsorption sites.