2-(Phenylazo)phenylboranes bearing several substituents were synthesized and substituent effects on their structures and photoisomerization behaviors were investigated to reveal the scope of the photoswitching of the coordination number of the boron by using an azobenzene-based photoresponsive ligand, 2-(phenylazo)phenyl group. 11 B NMR, X-ray crystallographic analysis, and UV–vis spectra revealed that electron-donating ability of the substituents at both the boron atom and the azobenzene moiety determined the strength of the interaction between the boron and the nitrogen of the azo group. Photoisomerization behaviors of 2-(phenylazo)phenylboranes are largely affected by the B–N interaction.