Increasing research efforts have been focused on developing next-generation propellants. In this work, we demonstrated that assembling zero-dimensional (0D) silver clusters with energetic ligands into 3D metal organic frameworks (MOFs) not only inherited the short ignition delay (ID) time of the alkynyl-silver cluster but also significantly increased the output energy. Among them, the open cationic framework of ZZU-363 incorporating counter NO3- ions achieved a considerably reduced energy barrier and eventually the shortest ID time (26 ms), together with the highest volumetric energy density (40.4 kJ cm-3) and specific impulse (263.1 s), which is far superior to traditional hydrazine-based propellants. The underlying mechanisms are clearly revealed by theoretical calculations. This work opens a venue to significantly enhancing the hypergolic activity of metal clusters and MOFs.