The formation of terraminopiperazinium salts using water as solvent provides a green, straightforward approach to highly energetic salts that exhibit good thermal stabilities and moderate densities. The N,N,N',N'-tetraaminopiperazinium cation was selected for this study because of its high nitrogen-nitrogen bond content and its hign positive near or formation. Theoretical and empirical calculations on energetic salts based on this nitrogen-rich cation reveal them to have high positive molar enthalpies of formation, as high as 1034.0 kJ mol(-1), supporting the application of these new salts as potential energetic materials.