To explore low sensitivity and environmental-friendly energetic combustion catalysts， three new energetic copper complexes， ［Cu（NH₃）₄（DN）₂］， ［Cu（IMI）₄（DN）₂］， ［Cu（ATO）₄］（DN）₂ were synthesized. Ammonium dinitramide （ADN） was used as a precursor to prepare dinitramide acid （HDN） by ion exchange reaction， and the resultant solution reacted with basic copper（Ⅱ） carbonate continually to produce copper（Ⅱ） dinitramide， which reacted further with nitrogen-rich ligands （ammonia， imidazole， 4-amino-1，2，4-triazole-5-one）. The structures of the three complexes were characterized accurately by X-ray single crystal diffraction， infrared spectroscopy and elemental analysis. Their thermal stability， hygroscopicity， sensitivities toward impact （IS）， friction （FS） and electrostatic discharge （ESD） were investigated. Furthermore， the effect of ［Cu（IMI）₄（DN）₂］ towards the burning rate of propellants were performed. Results show that the thermal stability of three complexes can meet the application requirement of solid propellants， and the initial decomposition temperatures are all higher than 140 ℃. The hygroscopicity of the complexes were improved obviously， which could be as low as 2%-5% of the precursor ADN. ［Cu（IMI）₄（DN）₂］ has the lowest sensitivity （IS 28.6 J， FS 0%， ESD 185 mJ） of the three complexes. With 4% of ［Cu（IMI）₄（DN）₂］， the burning rate of the basic formula propellants was increased by 27.7%， which was expected to be used as low sensitivity burning rate catalyst in high burning rate solid propellants.