Laser-induced fluorescence excitation and IR-UV double resonance spectroscopy have been used to determine the hydrogen-bonded structure of benzyl alcohol-ammonia (1:1) cluster in a jet-cooled molecular beam. In addition,ab initio quantum chemical calculations have been performed at HF/6-31G and HF/6-31G(d,p) levels for different ground state equilibrium structures of the cluster to correlate the calculated OH and NH frequencies and their intensities with experimental results. The broad red-shifted OH-stretching mode in the IR-UV double resonance spectrum suggests strong hydrogen bonding between the hydroxyl hydrogen and the lone pair of the ammonia nitrogen. The position and intensity distribution of the calculated NH and OH modes for the minimum-energy gauche form at HF/6-31G level have better correlation with the experimental results compared to other calculated ground state equilibrium conformers. These results lead to the conclusion that the minimum energy gauche form of the cluster is populated in the jet-cooled condition.