Historically, Hammett constants have been extremely effective in describing the influence of substituents on chemical reactivity and other physical and chemical properties, whereas variables derived from quantum chemical calculations have generally been less effective. Taking the experimental pK(a)s of substituted anilines as a representative physicochemical property, five ab initio quantum chemical indices are compared for effectiveness as one-parameter regression descriptors for pK(a). All of the tested descriptors performed well for a set of 19 mono-, 13 di-, and 4 trisubstituted anilines, and two performed somewhat better than the traditional Hammett sigma constants. Among the calculated quantities, the best representation of the aniline pK(a)s is produced by the minimum average local ionization energy on the molecular surface.