The electron donor-acceptor properties of 9,10-bis((E)-2-(pyridin-4-yl)vinyl) anthracene (BP4VA) are studied by means of surface-enhanced Raman scattering (SERS) spectroscopy and vibronic theory of resonance Raman spectroscopy. The SERS spectra recorded in an electrochemical cell with a silver working electrode have been interpreted on the basis of resonance Raman vibronic theory assisted by DFT calculations. It is demonstrated that the adsorbate-metal interaction occurs through the nitrogen atom of the pyridyl moiety. Concerning the electron donor-acceptor properties of the adsorbate, it is shown that the charge transfer excited states of BP4VA are not optically active, in contrast, an internal transition to an excited state of BP4VA, which is localized in the anthracene framework, is strongly allowed. The charge transfer states will be populated by an ultrafast non-radiative process, that is, internal conversion. Thus, irradiation of BP4VA interacting with an appropriate surface creates an effective charge separation.