The electronic structure of boron difluoride acetylacetonate and its three derivatives was studied using photoelectron and absorption spectroscopy, as well as the density functional theory. In a series of binuclear acetylacetonate complexes containing bridge-moieties of sulfur and selenium atoms, it was found an appreciable mixing of the π₃-orbital of the chelate cycle with atomic orbitals S 3p and Se 4p resulting in destabilization of the HOMO levels by 0.4–0.6 eV, in comparison with the monomer. The positively charged fragment C(CH₃)-CX-C(CH₃) causes the field effect, which leads to stabilization of the LUMO levels by 0.3–0.4 eV and C 1s-levels by 0.5–1.2 eV. An analysis of the research results on the electronic structure made it possible to determine the effect of substituents in the γ position on the absorption spectra, which is mainly determined by the electron density transfer from the chalcogen atoms to the chelate cycles. It is shown that the calculated energy intervals between electron levels correlate well with the structure of the photoelectron spectra of valence and core electrons.