CrAlVYN-Ag coatings were successfully deposited by introducing the elements of V and Ag into CrAlYN hard coatings. Their microstructure and mechanical property as a function of the annealing temperature were investigated from room temperature (RT) (∼25°C) to 800°C. Besides, the worn surfaces were analyzed after combined effects of temperature and friction to figure out the wear mechanisms at different temperatures. The coatings exhibited special surface morphologies and Ag diffusion after annealing at different temperatures. In addition, the x-ray diffraction results showed that the coatings suffered obvious oxidation once the temperature exceeded 600°C; as a result of this, the coating hardness decreased sharply. The friction coefficients were relatively high during the tribological tests from RT to 400°C because the abrasive wear mechanisms played a dominant role. The lower friction coefficients obtained at 600 and 700°C were mainly due to the self-lubricating mechanisms. However, the coating exhibited higher friction coefficient at 800°C, which was mainly ascribed to the severe oxidation wear of the coating.