The electronic structure and ionization processes of acetylacetonate and bromoacetylacetonate of boron difluoride were modeled using the method of outer valence Green's functions (OVGF). It was shown for boron difluoride acetylacetonate that for ionization energies exceeding 12 eV the OVGF method data (energies and a sequence of electronic levels, the electron density localization) differ significantly from the results of DFT calculations. Theoretical values of ionization energies from molecular orbitals with predominant contributions of atomic orbitals F 2p are higher by 1.6-2.2 eV than the corresponding Kohn-Sham energies shifted by the magnitude of the correction to the orbital energy. For all the considered electronic levels of both compounds, close theoretical values of the spectral intensities and good agreement between the results of calculations and the experimental data of the ultraviolet photoelectron spectroscopy method are observed.