Adsorption behavior of thiadiazole derivatives, 2,5-bis(ethyldisulfanyl)-1,3,4-thiadiazole (DTA), dimercapto-1,3,4-thiadiazole (DMDT) as anticorrosion additives at copper oxide surface were studied by first-principles calculations, weight loss, electrochemical and surface characterization techniques. The adsorption energies calculated by density functional theory (DFT) were less than 0.3 eV, DTA and DMDT physically adsorbed on the copper surface and cannot replace the oxygen atom at the top site of the Cu-O slab models. The predicted physically interaction of the corrosion inhibitor on the copper surface, which was basically consistent with the results of XPS analysis and surface microtopography. It was shown that in the presence of DTA and DMDT adsorbed on copper surface depress the reaction rate of anodic dissolution and cathodic hydrogen evolution and obey Langmuir isotherm. Surface findings indicated the inhibitor film formed at copper surface can block corrosion and improve hydrophobicity.