The effect of the imidazole derivatives on corrosion behavior of copper in acid rain solution was investigated. Electrochemical methods, quantum chemical calculations and SEM–EDS analysis was used during the work. Results show that inhibition efficiency of 1,1′-sulfonylimidazole, 2-mercapto-1-methylimidazole and 1,2-dimethylimidazole improves with the increase of inhibitors concentration. Surface analysis confirmed that a protective layer is formed on the electrode surface. SEM–EDS analysis of the copper electrode surface confirmed adsorption of inhibitor on active sites on electrode surface. Adsorption of inhibitors in acid rain solution follows the Langmuir adsorption isotherm. Quantum chemical calculations confirmed results obtained by electrochemical measurements.