The electronic structures of CuO and Cu2O have been investigated by resonant photoemission at the copper 3p threshold. The experimental data from CuO are compared with the results of a cluster calculation. From this analysis we confirm the dominant d8 character of the states between 8 and 16 eV, and that singlet and triplet final states behave quite differently at the (3p→3d) resonance. It is necessary to specify the multiplet state when calculating the d-d Coulomb interaction in this case since the total energy spread of the d8 multiplets is about 8 eV. The results confirm the charge-transfer nature of the band gap in CuO. The resonance behavior in Cu2O is explained in terms of strong O 2p–Cu 4(sp) hybridization.