NiCr-Cr3C2-BaF2/CaF2 is a commonly used self-lubricating composite coating prepared on the surface of the moving components operating at high temperatures. The role of oxidation in high-temperature friction and wear behavior was studied in NiCr-Cr3C2-BaF2/CaF2 composite coatings. The coefficient of friction and wear rate of as-sprayed composite coatings decreased with increasing temperature from 600 to 800 °C due to the formation of tribo-layer mainly containing BaCrO4 and CaCrO4. However, the wear resistance of coatings decreased significantly as the oxidation time increased at 800 °C. The supporting effect of the near surface on the upper tribo-layer was weakened due to the generation of voids near the surface of composite coating after prolonged oxidation. The present study helps further understand the failure mechanism of NiCr-Cr3C2-BaF2/CaF2 coating in long service and provides an insight into the interactions between oxidation and wear in the sliding interface for multi-phase composite coatings.