A simple, one-pot synthesis of 1,4,5,8,9,12-hexaazatriphenylene (HAT) derivatives with different symmetries and multiple, distinct functional groups was developed. HAT derivatives containing amine and amidine groups with C-3 symmetry and HAT derivatives containing amine, amidine, and nitrile functionalities with C-2 symmetry were obtained by reacting 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT(CN)(6)) with propyl amine and aniline, respectively. Crystal structure analysis, infrared spectra, and density functional theory calculations demonstrated that the amidine structures were stabilized by intramolecular hydrogen bonds.