A new method for preparing effective inhibition film on copper has been developed. Phenylthiourea was first adsorbed to a copper surface to form a self-assembled film. 1-Dodecanethiol was then self-assembled on the surface for subsequent modification. Finally, ac voltage was loaded on copper covered with the mixed film to further modify the film. After these procedures, an effective inhibition film was obtained as indicated by the low corrosion current density in polarization curves. High charge-transfer resistance in electrochemical impedance spectra reveals that the film hinders corrosion electrochemical reaction between the copper surface and NaCl solution. Film coverage on the copper surface is more than 99.0%, and inhibition efficiency is more than 97.2% in 0.5 mol dm(-3) NaCl solutions. The mixed films before and after ac treatment are stable in a wide region of potentials. X-ray photoelectron spectroscopy analysis reveals that the effect of ac treatment may associate with the formation of a new complex compound. (C) 2003 The Electrochemical Society.