These thermocouples are well-suited for measuring extremely high temperatures. Typical uses are hydrogen and inert atmospheres, as well as vacuum furnaces. They are not used in oxidizing environments at high temperatures because of embrittlement. A typical range is 0 to 2315 °C, which can be extended to 2760 °C in inert atmosphere and to 3000 °C for brief measurements.
Pure tungsten at high temperatures undergoes recrystallization and becomes brittle. Therefore, types C and D are preferred over type G in some applications.
In presence of water vapor at high temperature, tungsten reacts to form tungsten(VI) oxide, which volatilizes away, and hydrogen. Hydrogen then reacts with tungsten oxide, after which water is formed again. Such a "water cycle" can lead to erosion of the thermocouple and eventual failure. In high temperature vacuum applications, it is therefore desirable to avoid the presence of traces of water.
An alternative to tungsten/rhenium is tungsten/molybdenum, but the voltage–temperature response is weaker and has minimum at around 1000 K.
The thermocouple temperature is limited also by other materials used. For example beryllium oxide, a popular material for high temperature applications, tends to gain conductivity with temperature; a particular configuration of sensor had the insulation resistance dropping from a megaohm at 1000 K to 200 ohms at 2200 K. At high temperatures, the materials undergo chemical reaction. At 2700 K beryllium oxide slightly reacts with tungsten, tungsten-rhenium alloy, and tantalum; at 2600 K molybdenum reacts with BeO, tungsten does not react. BeO begins melting at about 2820 K, magnesium oxide at about 3020 K.