Three new boron difluoride complexes based on phthalazine–pyridine, denoted (6), (7) and (8), have been synthesized and their photophysical and electrochemical properties have been studied. Solutions of these new BF₂-complexes exhibit an intense blue fluorescence under UV light at low concentrations. Fluorescence quantum yields (QYs) have been determined by photoluminescence (PL) spectroscopy and decay times (τ) by semi-empirical methods. QYs of (6), (7) and (8) vary from 25% to 79%. HOMO and LUMO energy levels have been estimated by cyclic voltammetry and PL spectroscopy. The HOMO and LUMO energy levels, at ∼−5.3 eV and ∼−2.3 eV, respectively, make these new complexes interesting candidates as blue emitters in OLED applications.