Cr-W-N coatings with a Cr interlayer were prepared using reactive direct-current magnetron cosputtering on Si and cemented carbide substrates. To investigate the chemical inertness of Cr-W-N coatings against commercial moldable SiO 2 -B 2 O 3 -BaO-based glass in glass molding, thermal cycle annealing at 270 °C and 600 °C was performed in a quartz tube furnace in a 15-ppm O 2 -N 2 atmosphere. Variations in the crystalline structure, mechanical properties, and surface roughness after various annealing durations were investigated. The results indicated that Cr 37 W 31 N 32 and Cr 24 W 46 N 30 coatings maintained a face-centered cubic phase and exhibited superior mechanical properties and low surface roughness after up to 1000 thermal cycles; these properties were attributed to the formation of amorphous oxide scales. By contrast, Cr 8 W 69 N 23 and Cr 4 W 82 N 14 coatings with a nanocrystalline W phase in the as-deposited state formed WO 3 oxide scales after annealing, which negatively affected their mechanical properties and raised surface roughness values.