Multilayer coatings offer significant advantages in protecting materials’ surfaces by shielding the underlying materials hierarchically from damage and wear. The layering morphology and structure of multilayer coatings directly affect their wear resistance capacity. Using a systematic set of experiments and molecular dynamics (MD) simulations, we studied the effect of layering thickness on the macroscale wear response of DLC/WC multinanolayer coatings. Our study revealed the existence of a critical bilayer thickness where maximum scratch hardness and wear resistance can be achieved. Our large-scale MD simulations showed that reducing the WC layer thickness to a certain limit increases the scratch hardness due to the confinement of dislocation motion. However, when the thickness of the WC layers falls below 2 nm, the deformation mechanism transitions from the interface-induced dislocation confinement to the interface-mediated amorphization of WC layers, reducing the scratch hardness of the coating. This finding offers a procedure for optimizing the macroscale wear performance of multinanolayer coatings.