Fourier-transform Raman and infrared spectra were acquired for four arginine vasopressin (AVP) analogs contain- ing L -diphenylalanine (Dpa): [Dpa 2 ]AVP, [Cpa 1 ,Dpa 2 ]AVP, [Dpa 3 ]AVP, and [Cpa 1 ,Dpa 3 ]AVP (where Cpa denotes 1- mercaptocyclohexaneacetic acid). We compared and analyzed these spectra. In addition, the Raman spectra were compared to the corresponding surface-enhanced Raman scattering spectra recorded in an aqueous silver colloidal dispersion. Silver colloidal dispersions prepared by the simple borohydride reduction of silver nitrate were used as substrates. The geometry of these molecules etched on the silver surface was deduced from the observed changes in the intensity enhancement, breadth, and shift in wavenumber of the Raman bands in the spectra of the bound versus free species. Based on the obtained data, adsorption mechanisms were proposed for each case, and the suggested adsorbate structures were compared. All the molecules were thought to adsorb onto a silver surface via a phenyl ring, free electron pairs on the sulfur atom, and C Oand –CONH-bonds. However, the orientation of these fragments on the colloidal silver surface and the strength of the interactions withthissurfacearedifferent.For[Dpa 3 ]AVPand[Cpa 1 ,Dpa 3 ]AVP,astronginteractionamongthe – CCN-peptidefragmentand the colloidal silver surface occurs.