The structure of hyperbranched aromatic polyamides synthesized from different ratios of p-phenylenediamine and trimesic acid (A(2) + B-3 reagent pair) has been investigated by means of H-1 and C-13 NMR spectroscopy. On the basis of a detailed NMR signal assignment six 1,3,5-trisubstituted benzene moieties with different substitution patterns can be distinguished. The different monomer ratios influence the polymer architecture with respect to the content of these substructures, the degree of branching and the predominant functionalities (COOH or NH2). An excess of B-3 results in a larger number of branches and a predominant COOH functionalization. H-1 NMR proves site-specific interactions between lithium cations and the polymer substructures. The observed chemical shift effects simplify the quantification of the spectra. Finally, acetylation of amino groups by acetic acid, an impurity in commercial trimesic acid, could be proven.