Complex self‐assembled monolayers (SAMs) were prepared by modifying the adsorption of cysteine with dodecylacid (DAC) and with dodecylamine (DAM) on copper surfaces. Their protective effects against copper corrosion were investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in 0.5 M HCl aqueous solution. Results show that SAMs suppress cathodic current densities and shift the corrosion potential toward more negative values. Two types of complex SAMs enhance the anticorrosion effect of cysteine SAMs. PM3 semi‐empirical quantum calculations were used to obtain the quantum chemical parameters. The complex SAMs formed from cysteine and DAM have the higher EHOMO level and the better protection effect.