Density functional theory calculations have been preformed on a series of hydrogen-bonded complexes of substituted aliphatic and aromatic carboxylic acids with ammonia. Molecular properties, particularly those related to hydrogen bonding, have been carefully examined for their interdependence as well as dependence on the acidity of the acid. The bond length and stretching frequency of the hydroxyl group and the hydrogen-bond length and energy of the complex are shown to be highly correlated with each other and are linearly correlated with available literature pK(a) values of the carboxylic acids. The linear correlations resulting from the fit to the available pK(a) values can be used to predict the pK(a) values of similar carboxylic acids. The pK(a) values so predicted using the different molecular properties are highly consistent and in good agreement with the literature values. This Study suggests that calculated molecular properties of hydrogen-bonded complexes allow effective and systematic prediction of pK(a) values for a large range of organic acids using the established linear correlations. This approach is unique in its capability to determine the acidity of a particular functional group or the local acidity within a large molecular system such as a protein.