The friction reduction performance of WC-Co-Cr composite coatings at high temperatures is of great significance. In this study, a WC-10Co-4Cr-4CaF2 wear-resistant self-lubricating coating was prepared using HVOF. The microstructure, element distribution, and tribological properties of the coating at different temperatures were investigated. The introduction of the low-solid lubricant CaF2 had little effect on the microstructure and mechanical properties of the coating. The friction coefficient of the coating increased as the temperature increased, and the coating exhibited almost no wear at 400 °C. The dense composite oxide film was formed on the surface in the presence of high contact stress at 25 °C, significantly reducing the friction coefficient and wear amount of the coating.