Salts of bis(3,5-dinitro-1H-1,2,4-triazolyl)dihydro- and dichloroborate and bis(5-nitro-2H-tetrazolyl)-, bis(5-trinitromethyl-2H-tetrazolyl)-, and bis(5-fluorodinitromethyl-2H-tetrazolyl)dihydroborate anions have been synthesized by the treatment of hydroborates or chloroborates with the corresponding nitroazoles or nitroazolates, respectively. Alkali-metal salts of these dihydroborates are energetic and can be shock-sensitive, while salts with larger organic cations, such as NMe4+, PPh4+, or (Ph3P)(2)N+, are less sensitive. Poly(nitroazolyl)borates are promising candidates for a new class of environmentally benign energetic materials and high-oxygen carriers.