The mechanism of copper corrosion and its inhibition were studied using electrochemical techniques, in situ scanning tunneling microscopy (STM) and electrochemical quartz crystal microbalance (EQCM) methods. The morphological changes of Cu (111) were followed in 0.1 M Na2SO4 solution at pH 2.95. The adsorption of 5-mercapto-1-phenyl-tetrazole (5-McPhTT) at different concentrations was studied. The anodic dissolution of copper in 0.1 M Na2SO4 was clearly modified and hindered by the addition of 5-McPhTT. The anodic current density was reduced sharply due to the adsorption of the inhibitor on the metal surface thus providing protection. EQCM data revealed that the addition of the inhibitor to the aggressive solution did not cause a continuous increase in the electrode mass. This fact indicates that the inhibitor effect in hindering copper corrosion was due to the adsorption of a monolayer or even a submonolayer.