Eight kinds of energetic coordination polymers (ECPs) with multi-coordination were designed and synthesized by combining the carbonyl group with coordination potential in biuret with transition metal nitrates and perchlorates (Co2+, Ni2+, Cu2+, and Ag+). The structures of these complexes are confirmed by infrared spectroscopy, elemental analysis, and X-ray single-crystal diffraction. The physical and chemical performance test results show that the solvent-free ECPs 7 (Cu(BIU)2(ClO4)2) has the best performance (Tdec = 328 °C, D = 7600 km·s–1, P = 27.8 Gpa, IS = 25 J, FS = 240 N). Among them, ECPs 7 and 8 (Ag(BIU)ClO4) have good detonation performance during hot plate and laser ignition tests (ECPs 7: P = 15 W, τ = 6 ms, E = 80 mJ; ECPs 8: P = 20 W, τ = 5 ms, E = 100 mJ). The result shows that improving the oxygen balance of ligands and constructing multidentate coordination structures may be a new effective strategy for improving the performance of laser-sensitive ECPs.