The series of nine 2-benzoylmethylenequinoline difluoroborates have been synthesized and characterized by multinuclear magnetic resonance, X-ray diffraction (XRD), and computational methods. The through-space spin-spin couplings between 19F and 1H/13C nuclei have been observed in solution. The NMR chemical shifts have been correlated to the Hammett substituent constants. The crystal structures of six compounds have been solved by XRD. For two derivatives the X-ray wavefunction refinement was performed to evaluate the character of bonds in NBF2O moiety by topological and integrated bond descriptors.