In the chemical mechanical polishing (CMP) of Cu, the Cu surface is oxidized and is concurrently removed by the mechanical function of an abrasive. Surface oxidation can lead to severe surface corrosion, and to prevent this, a corrosion inhibitor is added to slurries. Accurate understanding of the competition between oxidation and passivation is essential for advanced Cu CMP technologies. In this work, layer formation on clean Cu surfaces in benzotriazole (BTA), H2O2, and BTA–H2O2 aqueous solutions was studied by in situ spectroscopic ellipsometry. Time changes of ellipsometric parameters are discussed with respect to BTA and H2O2 concentrations. It was found that the BTA adsorbs onto the Cu surface and the adsorbed BTA transforms into a Cu–BTA complex in about 3 min after the onset of adsorption. The BTA/complex layer passivates the Cu surface against oxidation by H2O2.