An in situ spectroelectrochemical investigation of the spontaneous potential oscillations, galvanically induced in the Cu-(II)-lactate and -tartrate systems, has been performed using confocal Raman microspectroscopy (CRM). The results, concerning both the Cu-(II)-lactate and -tartrate systems, show that the Raman background signal of the copper/cuprous oxide electrode exhibits an oscillating behavior with the same periodicity as the potential oscillations. This phenomenon most likely originates from the surface enhanced Raman scattering effect and the resulting deposit can be described as a layered composite made of copper and cuprous oxide where the relative content of each constituent is a function of the working electrode potential during the deposition process; mainly copper being deposited at the lower potentials and cuprous oxide at the higher potentials. Some aspects of the interaction of the organic anions with the growing surface are also discussed. (C) 2003 The Electrochemical Society.