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However, conventional catalytic promoters often exhibit suboptimal catalytic kinetics due to inefficient utilization of active sites. Herein, atomically dispersed Cu\u2010coordinated covalent organic frameworks (COFs)\u2010based catalytic promoters are reported, decorating with energetic anion groups. The highly accessible single Cu sites confined in the COFs significantly contribute to the raid and concentrated energy release of AP, yielding a sharply narrowed decomposition peak at 341.3\u00a0\u00b0C with a peak width of only 9\u00a0\u00b0C. This performance is markedly superior to the dispersed exothermic process of raw AP (410.3\u00a0\u00b0C with a peak width of 30\u00a0\u00b0C). Additionally, the energetic COF promoter considerably increased the output energy via collaboratively promoting the chemical energy release of AP and its own decomposition. Correlating in situ spectroscopies and theoretical calculations reveals that the incorporated anionic groups effectively modulate the local electronic structure of the Cu sites. This alteration promotes the key step of cleavage of Cl\u2500O bonds in AP intermediates to produce reactive oxygen species and also boosts the oxidation of NH\n                    <jats:sub>3<\/jats:sub>\n                    to high\u2010valence nitrogen oxides, thereby accelerating the combustion reaction kinetic.\n                  <\/jats:p>","DOI":"10.1002\/advs.202501761","type":"journal-article","created":{"date-parts":[[2025,5,14]],"date-time":"2025-05-14T03:40:03Z","timestamp":1747194003000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":24,"title":["Single Cu Atoms Anchored Energetic COFs as Combustion Catalytic Promoters toward Rapid and Concentrated Thermal Decomposition of Ammonium Perchlorate"],"prefix":"10.1002","volume":"12","author":[{"given":"Meng","family":"Zhang","sequence":"first","affiliation":[{"name":"Frontiers Science Center for High Energy Material Advanced Research Institute of Multidisciplinary 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