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Catalytic stability is the prerequisite for the catalyst to achieve high catalytic efficiency. This study finds a new path that Prussian Blue (PB) ultrathin nanosheet assembly material (PB‐NSa) is designed and used to reach efficient catalysis through continuous interaction with ammonium perchlorate (AP, component to be catalyzed). Based on the strong oxidation environment provided by AP, the decomposition of PB occurs in advance, the product Fe2O3 accelerates the decomposition of AP that can release a large amount of gas, then reacts on Fe2O3 and disperses it near the undecomposed AP, finally realizing continuous and efficient catalysis. The results show that under the catalysis of PB‐N, "deactivation" stage of AP thermal decomposition disappears, showing two consecutive exothermic stages, high temperature decomposition peak of AP is reduced to 341.1 °C, the reduction range is 73.1 °C. Combining kinetic calculation and TG‐IR test, it is found that PB‐NSa can keep excellent catalytic stability, which depends on its special structure and interaction with AP. This research provides a design idea for the material to achieve catalytic stability, which will greatly promote its rapid industrialization. [ABSTRACT FROM AUTHOR]