Silver antiquities can be tarnished easily by the actions of oxygen, sulfur compounds, humid and ultra-violet light in atmosphere. Silver tarnishing could result in pattern unclear on the surface of ancient artifacts. The composite corrosion inhibitors (PPM), composed of several azoles compounds such as 1-phenyl-5-mercaptotetrazole (PMTA), 2-mercaptobenzoxazole (MBO) and 2-mercaptobenzimidazole (MBI), were used to film pretreatment that could improve the antitarnishing abilities of silver antiquities obviously. The anti-tarnishing films were studied by using Auger Electron Spectroscopy (AES) and X-ray Photoemission Spectroscopy (XPS). Test results showed that the synergistic effect of silver anti-tarnishing was produced after treated with PMM, the anti-tarnishing film formed by PMM was more compact and stable than that of mono-component inhibitor, so the composite rarnishing inhibitors (PMM) were much more effective. This kind of anti-tarnishing film was formed by the interaction between silver surface atoms and corrosion inhibitors, the thickness of the composite film is about 20nm, in which the main constitution was PMTA – Ag surface complex, MBO and MBI could promote the interaction between silver and PMTA. The normal Raman spectra (NRS) of PMTA, MBO and MBI were measured. Surface-enhanced Raman scattering (SERS) was also used to study the surface filming processes of these azoles corrosion inhibitors for anti-tarnishing of silver, and the interactions between components of composite corrosion inhibitor and silver surface. The mechanism of anti-tarnishing of silver was also discussed. The experiments results show that there are strong interactions between corrosion inhibitors and silver surface. As constituents of the composite inhibitor with different cycle configuration took on different adsorption directions on the silver surface, the much more compact anti-tarnishing film was formed. In the pretreatment solution, weak acid pH value is beneficial to the adsorption of corrosion inhibitor and pretreatment time should not less than 120 min. Under the condition of cathodic polarization with additional potential less than 600mV in the test, in the pretreatment solution and the solution of sodium sulfide, the SERS response of composite corrosion inhibitors became stronger as the potential became lower. It is proved that the composite corrosion inhibitors can prevent silver tarnish effectively from corrosion medium.