The primary objective of the present investigation is to examine the effects of air annealing on the mechanical, tribological, and structural properties of multilayer CrN/CrTiSiN coatings. The deposition of CrN/CrTiSiN multilayer coatings on a Ti6Al4V substrate was carried out using CAE-PVD technique. Subsequently, the as-deposited coatings were subjected to annealing in ambient air environment at a temperature of 600 °C for 1 h. The characterizaion purposes were achieved by XPS, XRD, FESEM, nanoindentation, Rockwell-C adhesion tests, and pin-on-disk wear tests. The results suggest that the annealing process led to the development of new Cr2N, Cr2O3, and SiO2 phases. The coating hardness increased from 21.5 GPa to 25.3 GPa by annealing process. The findings from the pin-on-disc experiment indicate that the wear resistance of the annealed coating exhibited superior performance when compared to both the as-deposited coating and the substrate. The improvment could be attributed to the annihilation of the residual stress and the formation of new phases on the surface.