Herein, we prepared Fe(II), Zn(II), hydroxylammonium, and hydrazinium pentazolates and investigated their thermal behavior, decomposition kinetics, and thermodynamic activation parameters. The thermolysis of metal and non‐metal salts featured three and two mass‐loss stages, respectively, with the decomposition of pentazolate anions occurring at 105–135 °C. Moreover, metal salts exhibited higher thermal safety than non‐metal salts under the same conditions. Iron and zinc pentazolates decomposed at lower temperatures than sodium pentazolate, i. e., Fe(II) and Zn(II) ions promoted the decomposition of pentazolate anions. The obtained results demonstrate that the prepared compounds hold great promise as energetic catalysts for solid propellant decomposition.