A bimetallic MOF, CoNi(EIM)2(DCA)2 (1), containing an energetic 1-ethylimidazole (EIM) ligand and a hypergolic linker, dicyandiamide (DCA), was synthesized via a facile method. A fascinating three-dimensional reticular architecture was observed by single-crystal X-ray diffraction in this bimetallic MOF, whereas the corresponding monometallic compounds Co(EIM)4(DCA)2 (2) and Ni(EIM)4(DCA)2 (3) were in the mononuclear coordination mode. Uniformly distributed Co and Ni were observed in the bimetallic MOF crystals by SEM-EDS elemental mapping. Bimetallic MOF 1 was thermally stable and insensitive to mechanical stimuli and possessed an excellent energetic density (22.37 kJ·g-1). Using 1 as a hypergolic promoter, the ignition delay time of 1-butyl-3-methylimidazolium dicyanamide (BMIM DCA) was reduced from 53 to 37 ms, better than that of 2 and 3 as promoters, due to the synergistic catalysis of the bimetal. Furthermore, the thermal decomposition mechanisms of BMIM DCA with 1, 2, and 3 were studied by differential scanning calorimetry (DSC). 1 had the best catalytic performance in BMIM DCA thermolysis with a decrease in the decomposition temperature from 314.5 to 308.0 °C and a decrease in the activation energy by 16.3%. All results shed light on the better catalytic effect of the bimetallic MOF on ionic liquid hypergolic ignition than monometallic coordination compounds.