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The dilithium (1), disodium (2), dipotassium (3) and dicesium (4) salt as well as the calcium (5), strontium (6) and barium (7) salt of 5,5′‐bis(1‐hydroxytetrazole) were prepared and characterized including NMR‐, IR‐ and Raman spectroscopy, mass spectrometry, elemental analysis and differential scanning calorimetry. The crystal structures of 1, 2 and 4–6 were additionally determined by single‐crystal X‐ray diffraction. The sensitivities of the salts towards impact, friction and electrostatic discharge were determined by means of BAM (Bundesanstalt für Materialforschung‐ und prüfung) methods. The potential use of 1, 6 and 7 as coloring agents in pyrotechnical mixtures as well as the utilization of 3 and 4 as additives in near infrared (NIR) emitting pyrotechnical formulations was examined.