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We investigated the detailed electronic structure of a series of hole-doped delafossites CuCr 1−x Mg x O 2 (x = 0, 0.2, 0.3) using photoemission spectroscopy (PES), x-ray absorption spectroscopy (XAS) and band-structure calculations. We found inconsistent Cu/Cr valences and the character of a doped hole among the spectra of PES and Cu L 3 XAS. To explain this inconsistency, we propose a new electronic-structure model that includes electron configuration of a Cu-O-Cr charge transfer state.