The invention discloses an azotetrazole-based energetic compound with the composition of M(ATZ)(L)n question mark mH2O, wherein, M refers to Mn, Co, Ni, Cu, Zn or Pb; ATZ refers to 5, 5'-azotetrazole ion, L refers to 1, 10-o-phenanthroline or 2, 2'-dipyridyl, n refers to 1 or 2, and m refers to an integer or a decimal between 0 and 10. In the invention, the 1, 10-o-phenanthroline or the 2, 2'-dipyridyl is introduced into the M(ATZ) as an ancillary ligand to obtain a novel compound, thus integrating the characteristics of high efficiency, insensibility and environmental protection of a catalyst on the premise of the combustibility improvement of composite propellants. The azotetrazole-based energetic compound has the advantages of simple preparation method and accessible raw materials.