A one-pot protocol has been developed to obtain a series of luminescent heteroleptic diarylborinic complexes bearing the 2-fluoro-3-pyridyl and another aryl group attached to the boron atom chelated with a simple or functionalized 8-oxyquinolinato ligand. The tetrahedral geometry around the boron atom in all compounds has been established by the 11B NMR spectroscopy and/or X-ray diffraction technique. In the solution, the obtained complexes have emission maxima ranging from 502 to 525 nm at room temperature. The quantum yield of emission significantly depends on the type and position of the substituents in the 8-oxyquinolinato ligands and aryl rings. An interpretation of the experimental UV–vis absorption and emission spectral data is supported by theoretical calculations of the frontier molecular orbitals. Marcus theory was used to theoretically evaluate charge-transport properties of the obtained complexes.