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We present the results of an x-ray diffraction investigation of the formation of oxide on electropolished Cu͑111͒ surfaces, both in situ at pH 4.5 and in air. In both cases the oxide is found to be crystalline cuprite and epitaxially aligned with the substrate, but with two possible epitaxial orientations. We followed the progress of oxidation by monitoring the shapes of the diffraction peaks for the two orientations as a function of time and potential. There is a narrow potential region wheredoi:10.1063/1.478495 fatcat:rkzlqdvy3jatre3ox5ijf7ckpu