In CuO and Cu2O , Cu is in the +2 and +1 oxidation states receptively. If there is mixed valance of Cu present in your sample, you will observe the features corresponding to both the Cu+2 and Cu+1 in XPS spectrum, which you can distinguish easily from the value of the corresponding  binding energy.

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It can be distinguish by calculating binding energy difference between Cu2p3/2 and Cu2p1/2 positions. If it is < 20eV means Cu2O and > 20eV means CuO phase.

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https://www.surfacesciencewestern.com/wp.../sia17_biesinger.pdf