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In this study we analyze the Cu 2 p -XPS in La ₂ CuO ₄ , CuO and Cu dihalides using the single-site Anderson model with five filled bands. We take into account the multiplet coupling between a Cu 3 d hole and a core hole, and the anisotropic hybridization between the 3 d hole and O 2 p valence band holes. As a result we show that the multiplet structures due to the Cu (2 p ) ⁵ (3 d ) ⁹ electron configuration are strongly affected by the anisotropy of the hybridization.