<p>In order to develop Ni-Al intermetallic compound-based thermal spraying coatings with integrated anti-friction and anti-wear functions, the effects of vacuum heat treatment on the microstructure, composition, mechanical properties, and wide-temperature tribological behavior of the Ni₃Al-Ag-MoO₃-Cr₃C₂ composite coating were systematically studied. The results revealed that heat treatment at 600 °C facilitated the migration and diffusion of coating and matrix constituents, leading to enhanced homogeneity, densification, and cohesive/bonding strength of the coating. Moreover, it facilitated the release of residual tensile stress while improving the fracture toughness of the coating. A high-temperature solid-phase reaction occurred between Ni₃Al and MoO₃ resulting in a uniform distribution of spherical nano-sized Ni₃Mo and Al₂O₃ phases within the coating which played a crucial role in dispersion strengthening. The optimization of the coating microstructure, along with enhanced cohesive/bonding strength, and toughness, facilitates the rapid formation of a lubrication film on the worn surface and significantly enhances the wear resistance of the coating. Consequently, both the friction coefficient and wear rate of the coating are reduced to 0.55 ~ 0.19 and 1.82 ~ 8.06 × 10⁻⁵ mm³/(N·m), respectively. Notably, at 400 °C, there is an order-of-magnitude reduction in the wear rate of the coating.</p>