Benzene molecules were desorbed from an in vacuo aqueous liquid beam by direct irradiation of the beam with an IR laser tuned to the 2.85 μm absorption band of water. Spectroscopic interrogation of the desorbed benzene molecules was performed via 1 + 1 Resonance-Enhanced Multi-photon Ionisation (REMPI). Rotational contour analyses of the 610 vibronic transition of benzene were performed to determine the rotational temperature of those molecules ejected during the desorption event. At the peak of the desorption plume density, the rotational temperatures were found to be up to ∼100 K lower than that recorded for molecules spontaneously evaporating from the liquid surface. At longer IR-UV laser delay times the benzene rotational temperatures are found to return to those observed following spontaneous evaporation. No evidence of IR desorbed neutral or cationic benzene-containing clusters was observed. However, ionic clusters were observed to be formed after REMPI of the benzene monomer. Analysis of the benzene intensity and that of post-REMPI formed clusters as a function of IR-UV delay shows that number density and local translational temperature vary along the desorption plume.