The surface-enhanced Raman scattering (SERS) spectra of solvated lithium cations and tetramethylammonium ions ((CH3)4N+) adsorbed on silver electrodes from methyl acetate (MA) solutions are reported and compared to the normal Raman spectra (NRS) of the corresponding solution. Enhanced Raman intensities from both adsorbed Li(MA)4+ and the C-N symmetric and asymmetric stretching modes from adsorbed (CH3)4N+ ions have been observed. The SERS spectra are strongly dependent on the applied potentials. Both the Li(MA)4+ and (CH3)4N+ ions are coadsorbed with specifically adsorbed anions, e.g., Br-, but the solvated lithium ions appear to be replaced by (CH3)4N+ as the potential becomes more negative. A simple model is proposed to illustrate the surface processes. Enhanced intensity resulting from laser illumination during the oxidation-reduction cycle has been observed and is discussed.