Molecular acidity is an important physiochemical property essential in many fields of molecular studies, but an efficient and reliable computational approach to make accurate predictions is still missing. In this work, based on our previous studies to use gas phase electronic properties such as molecular electrostatic potential and valence natural atomic orbitals of the acidic atom and leaving we demonstrate here proton, that different approaches can be employed to tackle this problem. To that end, we employ 196 singly, doubly, and triply substituted benzoic acids for We that different the study. show two approaches are possible, one focusing on the carboxyl group through its localized electronic properties and the other on the substituting groups via Hammett constants and their additivity rule. Our present results clearly exhibit that with the linear models built from the singly substituted species, one can accurately predict the pK(a) values for the doubly and triply substituted species with both of these two approaches. The predictions from these approaches are consistent with each other and agree well with the experimental data. These intrinsically different approaches are the two manifestations of the same molecular acidity property, both valid and complementary to each other.