The NiCrAlY–Mo–Ag composite coatings were prepared by atmospheric plasma spraying. The tribological properties of the composite coatings were investigated from 25 to 900 °C in details. The tribo-layer formed on the worn surface of the composite coatings and influenced the tribological properties at different temperatures. The addition of silver could effectively decrease the friction coefficient and wear rate of the coatings at the wide range of temperature. The rubbing process could form the nickel molybdate and promote the formation of silver molybdate within the worn surfaces at high temperature. The synergistic lubricating effects of nickel molybdate and silver molybdate are attributed to the improvement of the tribological properties of coatings at high temperature.