The analysis of the proton magnetic resonance spectra of 2-methylphenol and of 4-chloro-2-methylphenol in benzene-d6 and CCl4 solutions yields spin–spin coupling constants over five bonds between the hydroxyl proton and the meta ring protons. These coupling constants are related to the intramolecular equilibrium between conformers in which the hydroxyl group is oriented cis or trans to the methyl group. The free energy difference between the conformers is 0.4 ± 0.1 kcal/mol, with the trans form being the more stable. The concentration dependence of the hydroxyl proton chemical shift of the chloro compound in CCl4 suggests that dimerization is relatively unimportant and yields rough values for the extent of self-association. It is argued that the derived free energy values refer to the intramolecular equilibrium for the monomers.