The experimental finding of pronounced high-order modes in surface-enhanced Raman scattering (SERS) is important for the validation of different contributions to its chemical mechanism and the development of a unified theory. Herein, the overtones up to the third order are observed for both totally and nontotally symmetric modes in the SERS spectra of 4,4′-diaminotolane adsorbed on silver nanoparticles. The theoretical calculations under the effect of Albrecht terms reproduced the experimental spectra with satisfactory good agreement. The dimensionless displacements were derived from the experimental spectra (in the range of 2000−3000 cm −1 ) and allowed us to explain the appearance of overtones from charge transfer (CT) and molecular excitations. The revealed contribution of the molecular excitation to the resonance Raman spectrum indicates that the CT-SERS spectrum is not solely the result of the Herzberg−Teller scattering process.