To determine the thermal kinetic triplets and elucidate the reaction mechanism of thin intumescent fire-retardant coatings (IFR) of steel structures, one efficient combined kinetic approach was implemented in this study. Thermogravimetric experiments were conducted in air atmosphere at four heating rates, and the whole IFR thermal degradation process was divided into two stages. The average activation energy values derived by model-free methods were 78.9 kJ/mol and 175.16 kJ/mol for Stage I (0<α < 0.2) and Stage II (0.2<α < 0.9), respectively. Furthermore, the linear Coats-Redfern (CR) and non-linear Masterplots models were applied to identify the possible reaction mechanism. It was found that the F3/2 mechanistic model was better suited to the main thermal degradation process. Then model reconstruction based on the F3/2 mechanism model was performed. The results showed that the reconstructed model had a strict linear relationship in the independence analysis and KCE analysis, along with a good agreement between the theoretical and experimental results. The current study provided new insights into the systematic thermal degradation mechanism of IFR, and the proposed kinetic model would be helpful for the thermal protection prediction for steel structure during fire.