Several novel GO-based bis-tetrazole energetic coordination polymers (ECPs) were designed and prepared by solvothermal method, which contain cobalt(Ⅱ) and nickel(Ⅱ) as coordination center, 5,5′-bis-tetrazole(H₂BT) and 5,5-bis-tetrazole-1,1-dioldehydrate (DHBT) as ligand. The coordination polymer crystal can be controlled through regulating the experimental conditions. Five typical promising catalysts of GO-Co-DBT、 GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT and β-GO-Ni-BT were characterized by XRD(X-ray diffraction), XPS(X-ray photoelectron spectroscopy), SEM(scanning electron microscope)/EDS(Energy Dispersive Spectrometer) and DSC(differential scanning calorimetry)-TG(Thermogravimetric Analysis) techniques. DSC-TG results of GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT indicate that GO-based bis-tetrazole energetic coordination polymers could reduce crystal defect, then lower the hot pot and improve thermostability, so the dicomposition temperatures of GO-Co-DBT, GO-Ni-DBT and GO-Ni-BT are all above 200 ℃. These ECPs as energetic catalysts have significant catalytic effect on thermal decomposition of AP and RDX. The reason can be that more O elements being transferred to react with NH₄⁺ results in increasing the yields of NH₃ and H₂O, which also made two decomposition peaks of AP overlap and the whole heat release increase. The heat releases of AP and RDX catalyzed by graphene-templated bis-tetrazoles are 2757.0 J·g^-1 and 2898.0 J·g^-1 respectively, which improve more than 50% compared with pure AP and RDX. The endothermic peak of AP corresponding to the crystal transformation is also reduced to 23.2 kJ·mol^-1. Prepared GO-based bis-tetrazole energetic coordination polymers could enhance thermostability and decomposition efficiency of AP and RDX.