This review is focused on consideration of effects of the nature of N,​N'- and N,​O-​bidentate ligands on the structure and optical properties of their B(III) complexes. It has been established that B(III) complexes with asym. N,​N'- and N,​O-​bidentate ligands, such as ortho-​hydroxyphenyl substituted azaheterocycles and heteryl-​β-​ketoimines, exhibit large Stokes shifts, enhanced intensity, and extended range for luminescence in solns. as well as in solid state, comparable with characteristics of the family of BODIPYs derivs. Complexes of some bidentate ligands can be considered as promising fluorophores for applications in biomedical imaging, electroluminescent, solar cell devices, and other fields