Organic fireproof plugging material (OFPM) has excellent flame retardance and is widely used in construction cable holes. In order to study the micro‐scale thermal behaviors and combustion performance of OFPM, thermogravimetric experiments were performed at five heating rates of 5, 10, 20, 40 and 60 K/min in air atmosphere. The results showed that polychloroprene, China clay and carbonate in OFPM were involved in the whole degradation process, which included four stages. In the first stage, polychloroprene was decomposed into the intermediate and HCl. Subsequently, the intermediate participated in the nonoxidative pyrolysis and combustion process in the second stage. The char generated from pyrolysis continued to burn completely, which can explain the complex process involving multiple peaks in this stage. The decomposition of China clay into metakaolin and H2O was responsible for third stage. The fourth stage was assigned to the thermal decomposition of carbonate. In addition, Shuffled Complex Evolution algorithm was used to optimize the kinetic parameters for the simplified four‐stage reaction scheme. The accuracy of the optimized kinetic parameters was verified by the comparison of experimental data at the extra heating rates. Finally, the combustion performance indices including ignition index, flammability index and comprehensive combustion index for the major components were calculated to evaluate the flame retardance of OFPM.

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