Raman and Surface-Enhanced Raman Scattering (SERS) spectra of protonated molecular forms of atenolol (ATE) and metoprolol (MET) were recorded, and the vibrational bands assigned by means of Density Functional Theory (DFT) based calculations. The adsorption geometry to the silver surface of the investigated drugs was derived by considering the Molecular Electrostatic Potential (MEP) map and the SERS surface selection rules. Both molecules are adsorbed through the oxygen atoms and π-electrons of the ring to the silver surface. The whole structure of the molecules lies on the metal surface with the aromatic ring in a tilted and flat orientation for ATE and MET, respectively.