The construction and modification of novel energetic frameworks to achieve an ideal balance between high energy density and good stability are a continuous pursuit for researchers. In this work, a fused [5,6,5]-tricyclic framework was utilized as the energetic host to encapsulate the oxidant molecules for the first time. A series of new pyridazine-based [5,6] and [5,6,5] fused polycyclic nitrogen-rich skeletons and their derivatives were designed and synthesized. Two strategies, amino oxidation and host-guest inclusion, were used to modify the skeleton in only one step. All compounds exhibit good comprehensive properties ( > 200 °C, ρ > 1.85 g cm, > 8400 m s, IS > 20 J, FS > 360 N). Benefiting from the pyridazine-based fused tricyclic structure with more hydrogen bonding units and larger conjugated systems, the first example of [5,6,5]-tricyclic host-guest energetic material triamino-9-pyrazolo[3,4-][1,2,4]triazolo[4,3-]pyridazine-diperchloric acid (), shows high decomposition temperature ( = 336 °C), high density and heats of formation (ρ = 1.94 g cm, Δ = 733.4 kJ mol), high detonation performance ( = 8820 m s, = 36.2 GPa), high specific impulse ( = 269 s), and low sensitivity (IS = 30 J, FS > 360 N). The comprehensive performance of is superior to that of high-energy explosive RDX and heat-resistant explosives such as HNS and LLM-105. has the potential to become a comprehensive advanced energetic material that simultaneously satisfies the requirements of high-energy and low-sensitivity explosives, heat-resistant explosives, and solid propellants. This work may give new insights into the construction and modification of a nitrogen-rich polycyclic framework and broaden the applications of fused polycyclic framework for the development of host-guest energetic materials.