Raman and surface-enhanced Raman scattering spectroscopy were used to follow the chemical modification of quercetin (QUC) on silver nanoparticles. Different metallic systems were fabricated to check the influence of the interface, in terms of electric charge or total available surface, on the catalytic change undergone by QUC. The effect of QUC surface coverage was crucial to reveal information about the different orientation and the interaction mechanism with the metal at different concentrations of this flavonoid. Surface-enhanced Raman scattering spectra of good quality of QUC were observed at concentrations down to 10–8 M. Chemical modifications in the presence of nanostructure metal surfaces include oxidation followed by a subsequent polymerization via a condensation of rings whereas different chemical species have been recognized under different experimental conditions. The assignment of the new species formed on the metal surface was conducted. Copyright © 2012 John Wiley & Sons, Ltd.