Potentiometric and NMR-pH titrations were carried out on four classical complexones to elucidate their overall and site-specific basicities. NMR-pH profiles and Bjerrum's functions were adjusted to compound-specific symmetries and appropriate evaluation methods were developed. Symmetry-modulated relationships between the macro- and microconstants were deduced and self-consistent sets of microconstants were determined. The inherent basicity of carboxylates surrounded by adjacent, intramolecular ammonium and carboxylate sites have been found to be in the range of 1.83-2.02logk units, which are reduced by 0.05-0.12logk units upon a nearby carboxylate protonation.