Density functional theory calculations have been preformed on a series of the hydrogen-bonded fluorophenol-ammonia and bromophenol-ammonia complexes. Intermolecular and intramolecular properties, particularly those related to hydrogen bonding, have been carefully analyzed. Several properties, such as the bond length and stretching frequency of the hydroxyl group, the hydrogen bond length and binding energy, are shown to be highly correlated with each other and are linearly correlated with known experimental pK(a) values of the halogenated phenols. The linear correlations have been used to predict the pK(a) values of all fluorophenols and bromophenols in the series. The predicted pK(a) values are shown to be consistent from different molecular properties and are in good agreement with available experimental values. This study suggests that calculated molecular properties of hydrogen-bonded complexes allow the effective and systematic prediction of pK(a) values for a large range of organic acids using the established linear correlations.