The design and synthesis of energetic materials (EMs) with high energy and reliable stabilities has attracted much attention in the field of EMs. In this work, we employed a strategy of the coordination polymerization of mild dicyanamide ions (DCA-), two isomeric ligands 1-methyl-5-aminotetrazole (1-MAT) and 2-methyl-5-aminotetrazole (2-MAT) to construct energetic coordination polymers (ECPs). Four new ECPs {[Co(DCA)2(1-MAT)2]·H2O}n1, [Cu(DCA)2(1-MAT)]n2, [Cd(DCA)2(1-MAT)2]n3 and [Cd(DCA)2(2-MAT)2]n4 were successfully synthesized through solvent evaporation routes. Compounds 1 and 4 display 1D chains, while 2 and 3 exhibit 2D-layered structures. Compounds 1-3 with the 1-MAT ligand all exhibit reliable thermal stabilities (> 200 °C). The calculated heats of detonation (ΔHdet) of 1-3 are all higher than 1.4 kJ g-1, which are higher than traditional explosive TNT (1.22 kJ g-1) and the reported ECP AgMtta (HMtta = 5-methyl-1H-tetrazole, ΔHdet = 1.32 kJ g-1). Furthermore, sensitivity testing demonstrates that 1-4 features low mechanical sensitivity to external mechanical action in contrast with the extremely sensitive azide-based ECPs [Cu3(2-MAT)2(N3)6]n. In addition, compound 2 shows hypergolic properties via an 'oxidizer-fuel' drop experiment, demonstrating its application prospects in the field of propellants. This work details an approach of synthesizing multipurpose ECPs with reliable stabilities by introducing mild dicyanamide anions into nitrogen-rich skeletons.