Oxidation of 1,1-dimethylhydrazine leads to the formation of (E)-1,1,4,4-tetramethyl-2-tetrazene (1). Compound 1 undergoes oxidative addition with chloramine (Cl–NH2) to form the (E)-1-aminomethylidene-1,4,4-trimethyl-2-tetrazenium cation (TAT+) as its chloride salt 2. Metathesis reactions of salt 2 with energetic anion-transfer reagents lead to the formation of ionic compounds based on the TAT+ cation and the following anions: nitrate 3, perchlorate 4, 5,5′-azobis(tetrazolate) 5·6H2O, picrate 6, and azide 7. The water of crystallization in compound 5·6H2O can be removed to form the anhydrous material 5. All compounds were characterized by analytical and spectroscopic methods, and the solid-state structures of salts 2, 3, 4, 5·6H2O, and 6 were determined by low-temperature X-ray crystallography. We used preliminary energetic testing to gain insight into the sensitivities of the materials towards impact and friction and we assessed their thermal stability by differential scanning calorimetry (DSC) measurements. Additionally, the heats of formation of the energetic compounds were computed by using quantum mechanical methods (CBS-4M) and these values were used to determine some performance parameters of interest for the pure compounds and for their formulations with an oxidizer. Lastly, we calculated the expected decomposition gases of the pure compounds as well as those of the mixtures with an oxidizer.