We have investigated the electronic structure of CaCu3Ru4O12 and LaCu3Ru4O12 using soft x-ray photoelectron and absorption spectroscopy together with band structure and cluster configuration interaction calculations. We found the Cu to be in a robust divalent ionic state while the Ru is more itinerant in character and stabilizes the metallic state. Substitution of Ca by La predominantly affects the Ru states. We observed strong correlation effects in the Cu 3d states affecting the valence band line shape considerably. Using resonant photoelectron spectroscopy at the Cu L3 edge we were able to unveil the position of the Zhang-Rice singlet states in the one-electron removal spectrum of the Cu with respect to the Ru-derived metallic bands in the vicinity of the chemical potential.