In this paper we review the characteristics of resonance Raman spectroscopy (RRS) which permit the simple coupling of a vibrational spectroscopic detection method with an electrochemical generation method. The applications of this approach to observing radical ions electrolytically generated in bulk solution as well as in the electrode diffusion layer are discussed. Finally, a new Raman intensity enhancement mechanism which permits one to observe the spectra of molecules adsorbed on an electrode surface will be described