Electronic structure and optical properties of boron difluoride dibenzoylmethanate BF2Dbm and its four derivatives were studied using X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy, and quantum chemistry (DFT and TDDFT). In a series of the studied compounds, the relationship of molecular design and optical properties has been revealed. At the transition from BF2Dbm to BF2Dbm(OCH3)2, the HOMO-LUMO energy gap decreases, resulting in a bathochromic shift of the optical spectra. Substitution of one methoxy group by the nitro group in BF2Dbm(OCH3)2 causes a decrease in the contribution of the chelate ring π-orbital in the LUMO, resulting in a lower value of charge transfer from the substituents to the chelate ring in the case of the first excited state, which determines the characteristics of the main absorption bands. The nitro group transition from the m- to p-position of the benzene ring causes a change in the nature of the main bands of the optical spectra due to the increase of the splitting value of the LUMO and LUMO+1 levels. The main band in the optical spectra of the complex containing the C10H7 group is associated with the charge transfer transitions.