The thermal degradation behaviors of PC/PMPSQ (polymethylphenylsilsesquioxane) systems were investigated by thermogravimetric analysis (TGA) under non-isothermal conditions in nitrogen atmosphere. During non-isothermal degradation, Kissinger and Flynn-Wall-Ozawa methods were used to analyze the thermal degradation process. The results showed that a remarkable decrease in activation energy (E) was observed in the early and middle stages of thermal degradation in the presence of PMPSQ, which indicated that the addition of PMPSQ promoted the thermal degradation of PC. Flynn-Wall-Ozawa method further revealed that PMPSQ significantly increased the activation energy of PC thermal degradation in the final stage, which illustrated that the PMPSQ stabilized the char residues and improved the flame retardancy of PC in the final period of thermal degradation process.