Current high temperature ceramics, such as ZrO2, Si3N4 and SiC, cannot be used at temperatures over 1600°C due to their low melting temperature or dissociation temperature. For ultrahigh temperature applications over 1800°C, materials with high melting points, high phase composition stability, high thermal conductivity, good thermal shock and oxidation resistance are needed. The transition metal diborides, mainly include ZrB2 and HfB2, have melting temperatures of above 3000°C, and can basically meet the above demands. However, the oxidation resistance of diboride monolithic ceramics at ultra-high temperatures need to be improved for the applications in thermal protection systems for future aerospace vehicles and jet engines. On the other hand, processing science for making high performance UHTCs is another hot topic in the UHTC field. Densification of UHTCs at mild temperatures through reactive sintering is an attracting way due to the chemically stable phase composition and microstructure as well as clean grain boundaries in the obtained materials. Moreover, the stability studies of the materials in phase composition and microstructures at ultra high application temperatures is also critical for materials manufactured at relatively low temperature. Furthermore, the oxidation resistance in simulated reentry environments instead of in static or flowing air of ambient pressure should be evaluated. Here we will report the concept, advantages and some recent progress on the reactive sintering of diboride–based composites at mild temperatures.