The present work was initiated to finalize resin for the development of thermal protection system (TPS) for the external surface of a polymeric composite rocket motor case made up of Carbon roving and Epoxy resin. The temperature on the outer surface of the composite case increases due to kinetic heating caused by aerodynamic drag and vehicle velocity. These rocket motor casings are functionally required only in the ascent phase of missile trajectory till motor action time and stage separation. Due to which the experienced heat flux is relatively less, and the temperature on the external composite case is in order of 250 °C - 300 °C depending on missile configuration & trajectory, unlike extreme thermal conditions on ablative nozzle liners exposed to rocket motor exhaust. The maximum allowable temperature in the present study for the Carbon-Epoxy case is 100 °C due to degradation in mechanical properties. The thermal protection system on the external surface will function as a heat-insulating layer based on the working mechanism of ablation. The resin of the thermal protection layer has a substantial impact on the manufacturing process and curing aspects, especially compatibility with the pre-cured carbon epoxy case layer. The generation of test results for thermal stability, cure characteristics and Tg for Epoxy resin has also been included in present studies as an additional objective that provides significant inputs for process development. The test results for Epoxy resin is also used as a basis for the finalization of resin for the thermal protection layer for processing aspects apart from its basic thermal stability characteristics. The ablative thermal protection working mechanism is based on the ablation phenomenon. In the case of ablation, resin plays a vital role due to pyrolysis and other thermal characteristics. In the present experimental studies, the Phenolic resin and Silicone resin are considered as candidate resin materials for ablative thermal protection system based on available literature and in house experience. The main objective of the present studies is to evaluate thermal stability, char yield after final decomposition through DSC and TGA techniques for both resins as these are fundamental characteristics needed for the present specific application. The test results for specific grades (formulation) of phenolic and Silicone resins are generated and compared. In the present work, the experimental studies to evaluate glass transition temperature (Tg), thermal stability, and cure characteristics for Epoxy resin is also carried through DSC. The test results of specific grade Epoxy resin provides a basis to assess thermal margins for resins selected for ablative thermal protection system and inputs for process development and design requirements. The scope of the present studies is aimed to finalize the resin system for external thermal protection of composite rocket motor case based on thermal characteristics test results and other compatibility aspects with the structural layer. [ABSTRACT FROM AUTHOR]