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Self-assembled monolayer of allylthiourea (AT) was first formed on copper surface. 1-Dodecanethiol (DT) was then self-assembled on the surface for subsequent modification: Finally, AC voltage was loaded on copper covered with the mixed film for further improvement. After these processes, an effective inhibition film was obtained as indicated by the high charge-transfer resistance shown in electrochemical impedance spectroscopy and low corrosion current density in polarization curves. The maximum coverage and inhibition efficiency for copper corrosion was 98.6% and 98.5%, respectively. The mixed film was stable in a wide range of potential before and after AC voltage treatment.