Sixteen four-coordinate boron complexes based on N,O-heterobiaryl chelating ligands have been obtained and characterized. These compounds exhibited the multicolor emission with good quantum yields, large Stokes shifts (up to 4987 cm−1), and relatively long fluorescence lifetimes in solution and solid state. The manipulation with structural fragments both in heterocyclic and naphthol moieties showed the prospects for tuning of the absorbance and emitting characteristics. The data of the photo- and chemical stability of the complexes allow us to recommend their use in the study of biological systems. © 2023.