Ultra-High Temperature Materials (UHTMs) are at the base of entire aerospace industry; these high stable materials at temperatures exceeding 1600 °C are used to manage the heat shielding to protect vehicles and probes during the hypersonic flight through reentry trajectory against aerodynamic heating and reducing plasma surface interaction. Those materials are also recognized as Thermal Protection System Materials (TPSMs). The structural materials used during the high-temperature oxidizing environment are mainly limited to SiC, oxide ceramics, and composites. In addition to that, silicon-based ceramic has a maximum-use at 1700 °C approximately; as it is an active oxidation process over low temperature and water vapor environment condition. However, a great emphasis is required for developing structural materials in oxidation and rapid heating environment where the temperature is greater than 1700 °C. This review covers briefly all main types of Thermal Protection Systems (TPSs) and all the materials are used to fabricate them with the maximum operational temperatures. Also, it covers the promised UHTMs (SiC, ZrB2, HfB2, SiB6 and B4C) which are currently using for several aerospace applications, especially for TPS. Besides, it discusses the oxidation of SiC, B4C, SiB6, ZrB2 and HfB2. Therefore, the carbides and borides of the transition metals, Zr and Hf have a high-melting temperature and good stability in forming high-melting temperature oxides. © 2020 Published under licence by IOP Publishing Ltd.