The hydrogen bond structure of the p-cyanophenol-water cluster has been determined in the ground and first excited electronic state by rotationally resolved UV spectroscopy. The water molecule is trans-linearly bound to the hydroxy group of the p-cyanophenol moiety, with hydrogen bond distances considerably shorter in both electronic states than in the similar phenol-water cluster. The structure of the cluster has been elucidated by ab initio calculations at various levels of theory and compared to the experimental findings. The barriers to internal rotation of the water moiety were determined experimentally to be 275 and 183 cm(-1) for the ground and excited state, respectively. Hydrogen bond distances and the energy barrier to water torsion correlate with the pK(a) values of different substituted phenols for both electronic states.