The protection for copper tarnish was developed by surface treatment method and volatile corrosion inhibiting (VCI) technology. The performance of surface treatment and VCI material is also examined in simulated test environment. Benzotriazole (BTAH) solution that contained molybdate showed best performance than others. Usage of VCI materials with surface treatment was more effective. The protection film foamed on the surface of copper was investigated by auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). Molybdate does not participate in the formation of the protective film but promotes the passivation effect. This facilitates the stabilization of the cuprous oxide film, and strengthens the adsorption of BTAH.