A PCM continuum model, at the DFT/B3LYP level, is used to Study the solvent and substituent effects on the conformers, intramolecular hydrogen bond (HB) enthalpies, (DeltaH(intra)s), and O-H bond dissociation enthalpies, (BDEs), in 2-substituted phenols, 2-X-ArOH, in the liquid phase. Two electron-donating (edg) and three electron-withdrawing (ewg) substituents are chosen, involved ill a variety of biochemical transformations. Seven solvents, differing in their H-bonding ability and polarity, are selected to model different environmental situations. Very good correlations are found between the computed R(O-H) and v(O-H) values in Solution for all non-HB 2-X-ArOH, showing, that the former can be used as an universal molecular descriptor for the latter and vice-versa. In all 2-X-ArOH. the HB parent conformer is the most stable in all media, closely matching frequency experimental data ill CCl4. However. for all 2-X-ArO.. the most stable conformer either forms a "reverse"-HB or a HB is not formed, due to the long distance or steric effects. Changes in the stability, in solution, are observed for some of the 2-X-ArO. conformers. The intramolecular HB-strength in solution, DeltaH(S.intra), varies significantly with the size of the HB ring formed and the nature of the substituents. Reasonable correlations, derived between the two energetic parameters (BDEaw.sol and DeltaH(S.intra)) and the solvent (E-N(T) and a), and/or molecular, [R(O-H) and v(O-H)] ones, allow for an approximate estimation of the two former from the four latter. 2-X(edg) decrease BDEs (hence, increase the antioxidant efficiency of the solute, too) in all media: 2-X(ewg) present an opposite result. Moreover, an isodesmic reactions study affords total stabilization effect (TSE) values (identical to the Delta[BDEaw]s), which are mainly governed by the stabilization of the phenolic radical (SPR) than that of the parent molecule (SPP). Quantitative correlations between the two effects in the TSE in both the gas and the liquid phases are also given. Unlike in the protic solvents, the better stabilization of the radical than the parent species. derived for the 2-X(edg)-ArOH in the aprotic, apolar, and/or low polar solvents, could account well for their smaller BDE(sol)s. An effective antioxidant in solution Should involve either one of the two edg in any one of the two latter solvents.