This study focused on the kinetic modeling of the thermal decomposition of sodium percarbonate (SPC, sodium carbonate-hydrogen peroxide (2/3)). The reaction is characterized by apparently different kinetic profiles of mass-loss and exothermic behavior as recorded by thermogravimetry and differential scanning calorimetry, respectively. This phenomenon results from a combination of different kinetic features of the reaction involving two overlapping mass-loss steps controlled by the physico-geometry of the reaction and successive endothermic and exothermic processes caused by the detachment and decomposition of H2O2(g). For kinetic modeling, the overall reaction was initially separated into endothermic and exothermic processes using kinetic deconvolution analysis. Then, both of the endothermic and exothermic processes were further separated into two reaction steps accounting for the physico-geometrically controlled reaction that occurs in two steps. Kinetic modeling through kinetic deconvolution analysis clearly illustrates the appearance of the net exothermic effect is the result of a slight delay of the exothermic process to the endothermic process in each physico-geometrically controlled reaction step. This demonstrates that kinetic modeling attempted in this study is useful for interpreting the exothermic behavior of solid-state reactions such as the oxidative decomposition of solids and thermal decomposition of oxidizing agent.