Herein, CrN/WC–12Co duplex coatings were fabricated using physical vapor deposition (PVD) and high-velocity oxygen fuel (HVOF) technologies. The microstructure, mechanical properties, and tribological behavior of these coatings were studied and compared with those of a single CrN film. Although the WC–12Co interlayer did not change the phase structure of the top CrN film, it significantly improved the hardness, Young's modulus, load-bearing capability, and bonding strength. The wear resistance of the CrN/WC–12Co duplex system was twice that of a single CrN film. Moreover, the WC–12Co interlayer changed the wear mechanism from fatigue and polishing wear of single CrN film to the polishing wear of CrN/WC–12Co duplex coating.