Ionization energies, excited state energies, and oscillator strengths of electron–dipole transitions are calculated within the framework of the SCF–Xα–DV quantum–chemical model of the Co(HCOCHHCO)3 model complex in order to interpret the photoionization and electronic absorption spectra of cobalt tris–β–diketonate. It is shown that the sequences of ionization and excitation energies calculated in the transition state approximation do not significantly differ from the sequence of energies estimated in the frozen MO approximation. The model absorption spectrum with a correction of 1.9 eV applied to the energy of the vacant π4 * orbital is in good agreement with our gas–phase absorption spectrum of Co(acac)3.