The potential-dependent surface enhanced Raman scattering (SERS) and generalized two-dimensional correlation analysis (G2DCA) methods were used to characterize three pyridine-alpha-hydroxymethyl biphenyl phosphine oxide isomers: (diphenylphosphoryl)(pyridine-2-yl) methanol (alpha-Py), (diphenyl-phosphoryl)(pyridine-3-yl) methanol (beta-Py), and (diphenylphosphoryl)(pyridine-4-yl) methanol (gamma-Py). The aforementioned compounds were deposited onto Ag, Au, and Cu electrode surfaces under different applied electrode potentials in an aqueous solution at physiological pH. On the basis of the enhancement, broadening, and shift in wavenumbers of individual bands, the geometry of the investigated molecules and influence of substituent position on the adsorption mode (in the alpha-(2-), beta-(3-), and gamma-(4-) positions), electrode type, and applied electrode potential were examined. It was found that the SERS spectra are dominated by bands assigned to phenyl (Ph) and pyridine (Py) ring vibrations. However, some differences in the arrangement of the aforementioned fragments were observed with changes to the type of the metal surface and the applied electrode potential. (C) 2015 Elsevier B.V. All rights reserved.