Thermally stable explosives are becoming more and more important nowadays due to their important role in the oil and mining industry. The requirements of these explosives are constantly changing. Picramate-based compounds are poorly investigated towards their energetic properties as well as sensitivities. In this work, 13 different salts of picramic acid were synthesized as potential energetic materials with high thermal stability in a simple one-step reaction and compared with commercially used lead picramate. The obtained compounds were extensively characterized by e. g. XRD, IR, EA, DTA, and TGA. In addition, the sensitivities towards impact and friction were determined with the BAM drop hammer and the BAM friction tester. Also, the electrostatic discharge sensitivity was explored. Calculations of the energetic performance of selected compounds were carried out with the current version of EXPLO5 code. Therefore, heats of formation were computed and X-ray densities were converted to room temperature. Some of the synthesized salts show promising characteristics with high exothermic decomposition temperatures. Especially, the water-free rubidium, cesium, and barium salts 5, 6 and 10 with decomposition temperatures of almost 300 degrees C could be promising candidates for future applications.