The infrared spectra of (phenol)(H2O) n + cluster ions (n = 1−4, 7, 8) have been recorded in the region from 2850 to 3800 cm-1. The method developed for this study (IR-PARI = infrared photodissociation after resonant ionization) allows sensitive IR spectroscopy of cluster ions from size-selected neutral precursors. The three-color laser scheme used for ion selection and dissociation consists of a two-color S0 → S1 → D0 ionization of a mass-selected cluster followed by IR photodissociation of the cluster ion. The IR spectra were taken by monitoring the photodissociation dip of the parent ion signal and by recording the rise of the −H2O fragment signal. The experimentally observed frequencies are compared to the results of ab initio calculations. No proton transfer is observed for the (phenol)(H2O)1,2 + clusters. In contrast to the S0 state, the structure of (phenol)(H2O)2 + turns out to be linear. In the case of the (phenol)(H2O)3,4 + clusters, linear and solvated structures are discussed. Within the solvated structures, proton transfer can occur between phenol and the water molecule, which is hydrogen-bonded to phenol. The observed fragmentation thresholds indicate proton transfer for (phenol)(H2O) n ≥ 4 + on the nanosecond time scale of our experiment. At least for the (phenol)(H2O)8 + cluster, the second solvation shell is full and a third solvation shell will be formed.