In order to explore the solid propellant combustion catalyst， a new type of bi-ligand containing energy complex ［Cu（MIM）₂（AIM）₂］（DCA）₂ was synthesized from 1-methylimidazole （MIM）， 1-allyl imidazole （AIM）， copper nitrate and NaDCA， and its structure was characterized by infrared spectroscopy， X-ray single crystal diffraction and powder diffraction. The thermal decomposition process of the energetic complex was analyzed by DSC and TGA. Within the temperature range of 40-500 ℃， there is a melting peak （peak temperature is 93.5 ℃） and an exothermic decomposition peak （peak temperature is 199.4 ℃） in DSC curve. The sensitivity test of the complex shows that the friction sensitivity and impact sensitivity are low and the operation process is safe. Comparing the bi-ligand ［Cu（MIM）₂（AIM）₂］（DCA）₂ with ［Cu（MIM）₄］（DCA）₂ and ［Cu（AIM）₄］（DCA）₂ catalyses on the thermal decomposition of AP， the results show that the bi-ligand complex has better catalytic effect， which advanced the exothermic peak temperature of AP by 88.8 ℃， increased the heat release from 782 J·g^-1 to 2458 J·g^-1， and lowered the thermal decomposition activation energy by 47.1 KJ·mol^-1， implying the potential application as a composite propellant catalyst .