Novel N,O-bidentate BF2 and BPh2 complexes have been prepared in good to excellent yields through coordination of 8-hydroxy-2-methylquinolines and 2-(2-hydroxyphenyl)-3H-quinazolin-4-ones with boron trifluoride etherate or triphenylborane under mild conditions. All complexes have been characterized by H-1, B-11 and F-19 NMR, mass-spectrometry and X-ray crystallography data. Some complexes have been found to exhibit a significant fluore.scence in acetonitrile solutions. Electronic and site effects of substituents in both heterocyclic and phenol fragments proved to have a profound impact on quantum yields.