This study utilized first-principles calculations to evaluate the interfacial work of separation (Wsep) in metal/CrN systems, revealing that the Cr(111)/CrN(111) interface exhibits the highest adhesion strength of 0.44 eV/Å 2, followed by the Zr(002)/CrN(111) interface with 0.37 eV/Å 2. This result is consistent with the Wsep value calculated for the Cr(210) crystal plane. Guided by these theoretical predictions, Cr/CrN and Zr/CrN multilayer coatings were synthesized via arc ion plating to enable systematic comparative analysis. Microstructural characterization demonstrated that Cr/CrN coatings exhibit superior surface integrity, characterized by diminished defect density and lower roughness. Nanoindentation tests confirmed enhanced mechanical properties in Cr/CrN, with hardness reaching 20.9 ± 0.3 GPa, elastic modulus of 342.6 ± 4.9 GPa, and improved plasticity indices. Additionally, Cr/CrN coatings displayed superior bonding strength of 33.6 N. Tribological analysis under varying loads revealed ultralow wear rates for both coatings at 10 N, which were attributed to nanocrystalline grain boundary strengthening and compressive stress effects. However, Cr/CrN demonstrated exceptional wear resistance under medium-load conditions, where the wear mechanism transitioned from adhesive to a combined adhesive-abrasive-oxidative mode. High-temperature oxidation tests further validated Cr/CrN's thermal stability through the formation of a protective Cr₂O₃ layer, in contrast to Zr/CrN's degradation via monoclinic ZrO₂ (m-ZrO₂) oxide formation. The experimental validation of Cr/CrN's superior interfacial compatibility and multifunctional performance aligns with its theoretically predicted high Wsep, thereby establishing a robust computational-experimental framework for the design of high-performance wear-resistant coatings.