This paper deals with the effects of PEG during Cu electrodeposition from an acidic sulphate solution. This investigation was carried out with electrochemical and spectroelectrochemical techniques. Potentiostatically grown layers were examined by scanning electron microscopy. Adsorption of PEG on the growing Cu surface can be inferred from electrokinetic, SERS and morphological evidence: variations of the estimated exchange current density, qualitative and quantitative differences in the potentiostatic transients, changes on the cathodic current efficiency, effects on the three-dimensional crystallisation mode under both compact and dendritic growth conditions, appearance of surface-enhanced PEG-related Raman bands. SERS spectra revealed cathodic reactivity of adsorbed PEG.