Diamond-like carbon (DLC) coatings enhance tool wear resistance across various temperatures. The sp 3/sp 2 bond ratio within DLC significantly impacts its properties and thermal stability. Elevated temperatures can alter DLC’s structure, while metallic elements and interlayers like chromium can modify its microstructure and performance. To evaluate the potential of W-DLC coatings with a chromium interlayer on 40CrMoV5-1 hot work tool steel under elevated temperatures, mechanical and tribological properties were assessed at room temperature and at temperatures of 100, 200, 300, 400, and 500 °C. Nanoindentation revealed a maximum hardness of 14.1 ± 1.3 GPa for the coating deposited at room temperature, attributed to a high sp 3 content confirmed by Raman spectroscopy. Hardness decreased to 9.3 ± 1.0 GPa at 400 °C due to graphitization. The elastic modulus remained relatively constant across all temperatures. Tribological tests indicated a low coefficient of friction (CoF) of 0.15 at room temperature, increasing to 0.35 at 100 °C. The CoF further rose to 0.5 at 200 °C, coinciding with increased graphitization. However, the CoF reduced to 0.45 and 0.35 at 400 °C and 500 °C, respectively, likely due to the formation of a WO 3 tribo-film and the protective effect of the chromium interlayer.