The dependence of the 13C, 15N, and 1H isotropic NMR chemical shifts on amine substitution of aromatic ring systems are examined both experimentally and by DFT/GIAO (density functional theory/gauge including atomic orbitals) methods. There are large, monotonic decreases in the chemical shifts at odd-numbered (ortho and para) pyrimidine ring positions which do not occur at the even-numbered (ipso and meta) atoms as amine groups progressively replace hydrogens at the latter positions. This behavior parallels the computed 2p z electron densities which for the pyrimidine series increase monotonically at N1, N3, and C5 but exhibit small changes at the C2, C4, and C6 positions. Identical trends are noted for the aminobenzenes. The ring atom chemical shifts and 2p z electron densities at ortho and para (but not meta) positions are quite sensitive to the orientations of the amine groups which are pyramidalized as the result of balance between delocalization with the ring and the use of strongly directed sp3 orbitals at the nitrogen. The calculated results show that the barriers to amine group torsional and inversion motions are low, but averaging the chemical shifts over these appears to be relatively unimportant. Differences between the DFT and Hartree−Fock-based chemical shifts show that electron correlation effects monotonically increase with the number of NH2 substituents.