2D materials have gained momentum for lubrication purposes, which holds specifically true under more severe conditions such as elevated temperatures. Among them, MXenes are a new family of 2D materials, which offer an excellent electrical conductivity, tunable surface functionality, and outstanding mechanical properties. In the past five years, MXenes have been significantly studied for tribological applications due to their ability to form easy-to-shear tribofilms with excellent wear resistance. However, little is known regarding MXenes’ tribological performance at elevated temperatures. Therefore, we systematically studied the tribological performance of spray-coated Ti3C2Tx coatings after thermal annealing at temperatures between 50 and 400 °C using linear-reciprocating ball-on-disc tribometry. Advanced materials characterization demonstrated that thermal annealing of MXenes results in the release of superficial and intercalated water, the removal of surface terminations, and the oxidation of Ti3C2Tx to TiO2. Consequently, the tribological performance of the annealed coatings deteriorated, which is particularly pronounced for thin coatings, high normal loads, and elevated annealing temperatures. Our results provide insight into the thermal stability of Ti3C2Tx coatings as well as the implications on their tribological performance.