Surface-enhanced Raman scattering (SERS) of 4,4'-azopyridine (AZPY) on silver foil substrate was measured under 1064nm excitation lines. Density-functional theory (DFT) methods were used to calculate the structure and vibrational spectra of models such as Ag-AZPY, Ag(4)-AZPY and Ag(6)-AZPY complexes with B3LYP/6-31++G(d,p)(C,H,N)/Lanl2dz(Ag) basis set. The Raman bands of AZPY were identified on the ground of analog computation of potential energy distribution. The calculated spectra of Ag(4)-AZPY and Ag(6)-AZPY models were much approximated to the experimental results than that of Ag-AZPY model. The DFT results showed that the angles between two pyridyl rings keep 0 degrees from AZPY to Ag-AZPY, Ag(4)-AZPY and Ag(6)-AZPY model. The energy gaps between the HOMO and LUMO changed from 363 to 1140nm for AZPY-Ag complexes according to the DFT results. An conclusion was conceived that chemical enhancement mechanism may play an important role in the SERS of AZPY on silver substrate.