Vibrationally mode-selected phenol cations (C6H5OH+ and C6D5OH+) were reacted with ND3 in a guided-ion-beam instrument. Integral cross sections and recoil velocity distributions are reported as a function of collision energy and vibrational state. Three reactions are observed. A small signal is found for the [PhOH:ND3](+) adduct at low total energies, indicating the formation of a very long-lived complex. The major reaction is H/D exchange, generating PhOD++ND2H. Exchange is similar to 40% efficient at low energies, strongly inhibited by collision energy, and strongly enhanced by excitation of PhOH+ vibrations. Recoil velocity distributions suggest that H/D exchange proceeds through a statistical complex at all energies. A precursor complex is invoked to explain the energy and vibrational state dependence. The endoergic proton transfer reaction is a minor channel at all energies, with dynamics intermediate between the direct and complex limits. Quantum chemistry and RRKM calculations are reported, providing an additional mechanistic insight.