This work presents near-infrared Raman spectroscopy (FT-RS) and surface enhanced Raman scattering (SERS) studies of three pyridine-a-hydroxymethyl biphenyl phosphine oxide isomers: (diphenylphosphoryl)(pyridin-2-yl)methanol (alpha-Py), (diphenylphosphoryl)(pyridin-3-yl)methanol (beta-Py), and (diphenylphosphoryl)(pyridin-4-yl)methanol (gamma-Py) adsorbed onto colloidal and roughened in oxidation reduction cycles silver surfaces. The molecular geometries in the equilibrium state and vibrational frequencies were calculated by density functional theory (DFT) at the B3LYP 6-311G(df,p) level of theory. The results imply that the most stable structure of the investigated molecules is a dimer created by two intermolecular hydrogen bonds between the H atom of the alpha-hydroxyl group (in up (HOU) or down (HOD) stereo bonds position) and the O atom of tertiary phosphine oxide (=O) of the two monomers. Comparison the FT-RS spectra with the respective SERS spectra allowed us to predict the orientation of the hydroxyphosphonate derivatives of pyridine that depends upon both the position of the substituent relative to the ring N atom (in alpha-, beta-, and gamma-position, respectively) and the type of silver substrate.