Structural, vibrational, and thermochemical properties of phenol-(H2O)(1-6) and phenoxy radical-(H2O)(1-4) complexes were calculated by using density functional theory. The insertion of a phenol molecule in a water cluster keeps some similarities with the addition of a water molecule. The interaction of the phenoxy radical with water clusters shows a strong dependence on the cluster size. The results are compared with theoretical and experimental data for the vibrational structure of phenol-water complexes and with thermochemical data for the phenol O-H bond dissociation enthalpy.