The gas-phase acidities of ca. 60 monosubstituted anilines (with acidity span of almost 50 kcal mol(-1)) have been calculated using density functional theory (DFT) at the B3LYP/6-311+G** level. At this relatively simple level of theory the calculated (Delta G(calc)) and available experimental (Delta G(exp)) acidities are in reasonable quantitative correlation according to the following equation: Delta G(obs) = a + b Delta G(calc), where a = 20.79, b = 0.942, n = 27, R(2) = 0.990, and s = 0.78 kcal.mol(-1). The slope is not far from its ideal value. Substituent effects on the acidities were dissected separately into those operating in the neutral acid molecule and in its conjugated anion using the isodesmic homodesmotic reactions. All in all, both forms, neutral and anionic, are contributing in combination to make up the gross acidity of anilines. However, the contributions of the anions into the gross substituent effects are much larger than the substituent effects in the neutral anilines. Some of the systems were used in testing a relatively new theoretical model, COSMO-RS (conductor-like screening model for real solvents), using it for the prediction of pK(a) values in DMSO. The method proved to be rather accurate for showing pK(a) trends (R(2) = 0.980 in DMSO). However, the predicted absolute pK(a) values were all somewhat lower (rmsd = 2.49 kcal.mol(-1)) than the respective experimental values.