The molecular geometry and vibrational frequencies of 4,4′-azopyridine (AZPY) were calculated using the density functional theory (DFT) methods. Fourier transform infrared (FTIR), fourier transform Raman (FT-Raman) and near-infrared surface-enhanced Raman scattering (NIR-SERS) spectra of AZPY on the silver foil substrate have been recorded. On the basis of the computed results, FTIR, FT-Raman and NIR-SERS bands were assigned. It is shown that the calculated and observed frequencies are in good agreement with each other for FTIR and FT-Raman spectra. Surface selection rules derived from the electromagnetic enhancement model were employed to infer the orientations of AZPY on the silver foil substrate surface.