BaZnCuO3 (BZC) was synthesized using the sol-gel method. The BZC was incorporated in reduced graphene oxide (rGO) to produce BZC/rGO composite. The synthesized catalysts were characterized using Raman, powder X-ray diffraction (XRD), and Ultraviolet-visible (UV-Vis) analysis. The comparative effect of BZC and BZC:rGO composite was studied on the thermal decomposition of and 3-nitro-3H-1,2,4-triazol-5-one (NTO) and Ammonium Perchlorate (AP) using simultaneous Thermo-gravimetric technique (TG-DTA). BZC was a better catalyst for decreasing the thermal decomposition temperature and the thermo-kinetic parameters of both AP and NTO compared to BZC/rGO composite. BZC can reduce the thermal decomposition of AP and NTO by 121 oC, and 46 oC, respectively. The findings support BZC as a possible catalyst in the thermolysis of both NTO and AP.