The polarized Raman spectra in different environments along with the IR counterpart of 4-benzoylpyridine (4-BOP) were critically analyzed to assign all of its normal modes of vibration. The knowledge of the positions of different excited electronic states (EESs)was obtained from the study of electronic absorption spectra. Measurement of Raman excitation profiles (REPs)of several normal modes was carried out to get insight into structural and symmetry properties of the molecule. All the experimental observations were substantiated and corroborated theoretically by quantum chemical calculations (QCCs). The possibility of exciton splitting of the 1La band has been explored both from theoretical and experimental points of view. Copyright © 2010 John Wiley & Sons, Ltd.