The paper describes a DFT/B3LYP study, in the liquid phase, [using the PCM continuum model] on the O-H bond dissociation enthalpy (BDE) and ionization energy (IE) parameter values of the 2-monosubstituted phenols (2-X-ArOH), related to the H-atom transfer (HAT) and single-electron transfer (SET) mechanisms. The solvent and substituent effects on the conformers, the BDEs, and the IEs were studied using four electron-donating (EDG) and five electron-withdrawing (EWG) groups, in seven different solvents. In both the EDG-and/or EWG-substituted species of the parent compounds, radicals, and/or cation radicals, the most stable conformer is varied, depending on the medium and the substitution. The EWG-substituents increase IEs, resulting in a weaker antioxidant activity than the EDG ones; the effect appears stronger on the IEs than on BDEs. However, although the liquid-phase IEs, which are related to solution-phase oxidation potentials, decrease with the polarity and/or the hydrogen-bonding ability of the solvent, the opposite holds true for the BDEs, exhibiting a weaker effect. The gas-phase-calculated IE for benzene is among the most accurate ones in the field, compared to the experiment, that for phenol being the most accurate. In addition, calculated IEs for the 2-X-ArOH are in close agreement with the very few existing experimental ones. It is shown that the oxidation potentials are (a) highly correlated with the gas-phase ones, and (b) strongly solvent dependent. The stabilization/destabilization of the cation radical (SPC) contribution, in all media, is the decisive factor in the Delta IE calculation. The reasonable correlations found between the Delta BDE and Delta IE could account well for the assumption of the simultaneous action of both mechanisms in the 2-X-ArOH, in both the gas and the liquid phase. It seems, however, that the presence of a particular solvent by itself is not sufficient enough for the HAT to SET transition. The involvement of specific ED and/or EW groups in the 2-X-ArOH seems also necessary. It appears that our theoretical approach is not only generally applicable to the set of substituents important to antioxidant activity but also useful in (a) the rational design of phenolic antioxidants and (b) affording accurate BDE and IE parameter values related to both possible antioxidant mechanisms.