Burning rate of solid propellants can be effectively improved by adding catalysts and using smaller size ammonium perchlorate (AP). Although few reports, the exploration of changing the size of AP primary particles by catalysts is of great significance for improving combustion performance. Here, taking Co-bipy as an example, the potential advantages of such materials as AP decomposition catalysts are reported. Due to the existence of NO 3 − combined with oxygen rich environment provided by AP, the structural self-transformation from micronrods to nanoparticles can be quickly realized during the heating process. More importantly, when Co-bipy decomposes, it can play the role of "scalpel" and in situ cut AP particles. Results show that high-temperature decomposition of Co-bipy/AP occurs at 305.8 °C, which is 137.5 °C lower than that of pure AP. Catalytic mechanism is discussed by in situ IR and TG-IR, CoO can effectively increase the content of reactive oxygen species and weaken the N-H bond, realizing the rapid oxidation of NH 3 . Eventually, the behavior of Co-bipy cutting AP particles is tested. This interesting catalyst structure self-transformation behavior can not only realize the influence on AP, but also perform a positive function in the combustion process of solid propellants, such as opening the adhesive AP interface.