Perovskite energetic materials have recently attracted considerable attention owing to their high density, outstanding detonation performance and simple synthesis. However, the reported perovskite energetic materials exhibit an extreme imbalance between energy, thermostability and safety, which limits their practical applications. In this work, by introducing a planar [5,5] fused-ring framework into the B-site of a perovskite system through a simple one-pot assembly, a novel ABX3-type compound, BPP, is obtained. The target compound BPP exhibits high density (ρ = 1.88 g cm−3), excellent thermal stability (Td = 305 °C), and competitive detonation performance (D = 9042 m s−1), comparable to HMX and superior to that of RDX, together with relatively balanced impact and friction sensitivities (IS = 6 J, FS = 144 N). This work provides a new design paradigm for perovskite energetic materials with balanced energy, thermostability and safety, and demonstrates their great potential as candidates for next-generation high-energy-density materials (HEDMs).