2‐Nitrimino‐5,6‐dinitrobenzimidazole (1) was synthesized by nitration of 2‐aminobenzimidazole at ambient temperature in good yield. In order to explore new insensitive explosives four energetic nitrogen‐rich 1 : 1 salts such as the guanidinium (1a), aminoguanidinium (1b), triaminoguanidinium (1c) and hydroxylammonium (1d) were synthesized either by facile acid/base or in situ metathesis reaction. In addition 2‐nitrobenzimidazole (2) was synthesized by the reaction of 2‐aminobenzimidazole using potassium hyperoxide in THF. Different nitration methods were tested to obtain a theoretically 2,4,5,6,7‐pentanitrobenzimidazole but only the already known 4,5,6,7‐tetranitrobenzimidazol‐2‐one (3) could be isolated. All synthesized compounds were characterized especially by low temperature X‐ray diffraction, CHN elemental analysis and 1H and 13C NMR spectroscopy. The heat of formation of all new synthesized compounds was calculated using CBS‐4M electronic enthalpies in combination with the atomization method to calculate their detonation parameters with the EXPLO 5 V5.05 computer code.