The application of corrosion inhibitors is one of the most effective methods developed to inhibit the corrosion of Cu interconnects. The performance of potassium oleate (PO) as a potential corrosion inhibitor for copper in EDTA-H2O2 based solution was examined under alkaline environment. The inhibition efficiency and mechanism were studied by electrochemical characterization, surface morphology technology and molecular computing technology. Firstly, the water solubility and toxicity of PO were comprehensively evaluated. The results of electrochemical assessment manifest that the corrosion inhibition efficiency of PO for Cu can reach approximately 98.24%, even at relatively low concentration of PO (0.01 wt%), additionally, PO is a mixed-type corrosion inhibitor, which can effectively inhibit the corrosion circumstance of Cu in alkaline medium. These excellent performances are attributed to the physical and chemical properties of PO adsorption films formed by PO, which follows the Langmuir adsorption isotherm. Besides, Density Functional Theory (DFT) and molecular dynamics (MD) approaches were introduced to explore the most stable adsorption configuration and the most active adsorption sites.