New energetic salts (2, 3, 9, 10, and 11) were synthesized via the protonation of 4,4'-bi(1,2,4-triazole) or N-4(1,2,4-triazole)-N-3-(4-methyl-1,2,4-triazole)amine with nitric acid or perchloric acid or 5-nitro-tetrazole. The structures of 4,4'-bi(1,2,4-triazolium) nitrate (2), N,N-dimethyl-N'-(5-methyl-tetrazole)methanimidamide (8), and N-4-(1,2,4-triazole)-N-3-(4-methyl-1,2,4-triazolium)amine perchlorate (10) were confirmed by a single-crystal X-ray analysis. The physical properties and heats of combustion of the new ionic salts were measured, and the heats of formation were also determined.