The pyridine-borane (PyBH 3 ) complex was analyzed by Raman vibrational spectroscopy and density functional theory to elucidate its structural and vibrational properties and to compare these with those for neat pyridine (Py). The borane–nitrogen (BN) bond length, the BN dative bond stretching frequency, and the effects of dative-bonded complex formation on Py are presented. Rather than having a single isolated stretching motion, the complex exhibits multiple BN dative bond stretches that are coupled to Py’s vibrations. These modes exhibit large shifts that are higher in energy relative to neat Py, similar to previous observations of Py/water mixtures. However, significantly higher charge transfer was observed in the dative-bonded complex when compared to the hydrogen-bonded complex with water. A linear relationship between charge transfer and shifts to higher frequencies of pyridine’s vibrational modes agrees well with earlier observations. The present work is of interest to those seeking a stronger relationship between charge-transfer events and concomitant changes in molecular properties.