Ab initio (RHF, MP2, CASSCF, and CASPT2) calculations have been performed for the electronic ground and lowest excited singlet states of phenol, the complexes of phenol with water and ammonia, and the corresponding cations. In agreement with recent experiments it is found that proton transfer is a barrierless process in the phenol-(H2O)(3) and phenol-NH3 cations, whereas no proton transfer occurs in the phenol-H2O cation. Novel aspects of the reaction dynamics in the excited-state manifold of the neutral clusters are revealed by the calculations. Predissociation of the S-1(pi pi*) state by a low-lying (1)pi sigma* state leads to a concerted and proton-transfer reaction from the chromophore to the solvent. The excited-state reaction is endothermic in phenol-H2O and phenol-(H2O)(3) clusters but exothermic (though activated) in the phenol-NH3 complex. These results substantiate recent reinterpretations of spectroscopic and kinetic data on hydrogen-transfer reactions in phenol-ammonia clusters. The close relationship of the concerted electron-proton-transfer process in phenol-water complexes with the formation of hydrated electrons in the photolysis of phenol and tyrosine in liquid water is pointed out.