The ever-growing number of space launches triggering an enormous release of metallic dead weight into the atmosphere has become a global concern. Despite technological advancements, the inclusion of environmental concerns in space research has become the need of the hour. Here, we report the impact of iron oxide (Fe2O3)-doped polymeric carbon nitride (gCN) composites with varying metal contents (namely, GF1, GF2, and GF3 with iron contents of 0.1, 0.25, and 2 mmol, respectively) as a new class of catalysts for ammonium perchlorate (AP) thermolysis. Morphology studies revealed the dendritic morphology of the synthesized Fe2O3, and X-ray photoelectron spectroscopy (XPS) analysis confirmed the effective interaction between Fe2O3 and gCN in the composites. Among all of the synthesized composites, GF2 shows superior catalytic competence toward AP decomposition by amalgamating the double-stage decomposition process into a single stage followed by a considerable decrease in the decomposition temperature. The kinetic parameters calculated for the thermal decomposition of AP with and without catalysts using the KAS method substantiated the above results by significantly reducing the activation energy from 173.2 to 151.7 kJ/mol. Later, thermogravimetric and mass-spectrometric (TG-MS) analysis gives a clear idea about the catalytic efficiency of the synthesized catalyst GF2 toward AP decomposition from the accelerated emission of decomposition products NO, NO2, Cl, HCl, Cl2, and N2O in the presence of GF2. In a nutshell, gCN/Fe2O3 will open up new horizons in the field of synthesis of new catalytic systems with minimal metal content for composite solid propellants.