Corrosion inhibition effect of AHA film formed on the copper surface by self-assembled monolayers technique was estimated in 3 wt% NaCl solution by electrochemical impedance spectroscopy and polarization methods. Polarization data indicated that AHA was an anodic inhibitor. The maximum inhibition efficiency reached 93.5% in the case of assembly 3 h in 10 mM AHA solution. The adsorption of AHA on the copper surface fits Langmuir adsorption isotherm. Surface-enhanced Raman scattering together with quantum chemical studies demonstrated that N-O and C=O groups were attached to the copper surface, predicting the feasible adsorption centers and confirming the relationship between the molecular structures of AHA and its inhibition property.