The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrCx/a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar+CH4 glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr3C2 and Cr7C3 and structural transformation of the a-C:H matrix phase towards higher sp(2) bonding contents at temperatures above 450 degrees C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 degrees C. Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of similar to 0.13 for T= 200 degrees C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 degrees C. (C) 2007 Elsevier B.V. All rights reserved.