Abstract: For space exploration, high-performance and reliable passive thermal protection materials are among the key enabling technologies for entry and reentry spacecraft to safely accomplish their missions. This paper systematically reviews the development history and engineering applications of ablative thermal protection materials, ranging from early high-density systems to modern lightweight and high-efficiency systems. Typical thermal protection materials, including AVCOAT, PICA, and NF, are summarized, with an emphasis on their material characteristics, engineering applications, and technological evolution. Furthermore, recent research progress on thermal protection materials for extreme thermal environments, reusability, flexible/deployable structures, and multifunctional integration is discussed. Finally, future development trends for thermal protection materials in space exploration are outlined to provide a reference for the development and engineering application of advanced thermal protection materials in China.