A new energetic coordination polymer (ECP) composite, namely GO-Cu(ii)-AmTZ, has been synthesized by 3-amino-1,2,4-triazole (AmTZ) and multifunctional graphene oxide (GO) coordination with Cu(ii) successively. The ECP composite was further characterized through SEM, EDS and XPS analysis as well as FTIR and Raman spectroscopy. It shows high thermostability, high decomposition heat release and insensitivity to mechanical stimuli. What's more, thermal analysis data for ammonium perchlorate (AP) have been obtained by mechanically mixing GO-Cu(ii)-AmTZ and AP. The low-temperature decomposition (LTD, 335.3 °C) and high-temperature decomposition (HTD, 441.3 °C) peaks of AP were reduced to an exothermic peak at 298.4 °C at a heating rate of 10 °C min-1. GO-Cu(ii)-AmTZ exhibits outstanding catalytic performance by decreasing the activation energy from 168.7 kJ mol-1 to 122.4 kJ mol-1, indicating its promising application as a combustion catalyst for improving the thermal-catalytic decomposition performance of energetic materials largely. In addition, thermal analysis techniques including thermogravimetry coupled with mass spectrometry (TG/MS) and thermogravimetry coupled with infrared spectrometry (TG/IR) were employed to determine the decomposition mechanisms.