In this study, new highly energetic coordination polymers (ECPs) were successfully prepared by a facile chemical modification method based on functionalized graphene oxide (GO) sheets. Simple cross-linked GO layers with triaminoguanidine ligand (T) may further be bonded with crystals containing T and transition metal ions (T-M) using cobalt, zinc, silver, or iron as coordination centers, generating 2D-layered energetic hybrid ECPs crystals. Successful functionalization of the prepared ECPs was confirmed by SEM, exhibiting very small crystals (<400 nm). The thermal decomposition of the different T-M complexes, with or without GO-T, was assessed by using simultaneous differential scanning calorimetry and thermogravimetric analysis. It has been revealed that the coordination reaction of GO-T with T-M leads to the production of highly thermostable ECPs. Furthermore, the incorporation of 10% of functionalized GO has improved the thermal stability of T-M crystals. Raman spectroscopy demonstrates that both D and G bands of these new ECPs have been shifted. The different chemical bonding is also confirmed by FTIR and XRD analyses. The catalytic effect of the designed GO-T-M--T energetic composites on the decomposition of ammonium perchlorate (AP) and 1,3,5-trinitro-1,3,5-triazinane (RDX) has been investigated. The results confirmed that those ECPs have strong catalytic effect on decomposition of AP, and it may even stabilize RDX crystals before its thermolysis.