Two series of both nitrogen-rich and thermostable energetic materials as well as their energetic salts based on hetarenecarboxylic acids are now described. Among these new compounds, neutral compounds 3 and 10 have higher nitrogen contents (69.66% and 63.05%) than their energetic salts, which suggests that they could be used as green energetic materials. In addition, compound 3 shows a good decomposition temperature (T_d = 281 °C), which is close to that of TNT (T_d = 295 °C). Nitrogen-rich salt 6 exhibits better integrated energetic-properties (D = 8913 m s⁻¹, IS = 24 J, FS = 320 N) than RDX (D = 8795 m s⁻¹, IS = 7.5 J, FS = 120 N).