In this study, we present a potential method to predict the highest surface temperature reached during the heating by Raman analysis for CFRP ablator, which is commonly used in aerospace fields as a material of thermal protection system. The specimens are heated using various treatments such as static heating and dynamic heating by arc jet in inert and active environments followed by Raman analysis. The results obtained in this study indicate that the relationship between the highest surface temperature and the Raman parameters is independent of the heat treatment. The estimation method suggested for the highest surface temperature is based on Raman spectroscopic analysis.