The mechanisms of chalcopyrite oxidation in alkaline solutions have been studied using cyclic voltammetry and impedance spectroscopy techniques. The cyclic voltammetry was used to elucidate oxidation/reduction reactions, whereas impedance spectroscopy was used for in-situ characterization of the interface. To analyze the impedance spectra, equivalent circuit models were constructed based on a layer-wise growth of reaction products. Parameters of the equivalent circuit were calculated by comparing the experimental spectrum with that expected on the basis of equivalent circuit. From the value of equivalent circuit parameters, properties of the surface layers were inferred. These properties change substantially with the change in oxygen and/or collector concentration in solution. From such changes the effect of oxygen and collector concentration on the contact angle and flotation behavior of chalcopyrite were interpreted.