The in-situ formation of oxides on alloy surface induced by high temperature can effectively reduce wear and resist oxidation. In consideration of the solid solution strengthening effect and great oxidation resistance of additional elements at elevated temperature, the NiCrWMoCuCBFe coating was prepared by high velocity oxygen flame (HVOF) spraying technology, and its tribological behavior was scrutinized from 25 to 800 °C. By means of high temperature Vickers hardness tester and high temperature X-ray diffractometer, the mechanical properties and microstructures of NiCrWMoCuCBFe coating were measured. And the effect of the mechanical properties and microstructures of the coating on tribological performance was discussed in detail. The results showed both its friction coefficient (0.37) and wear rate (5.067 × 10⁻⁶ mm³·N⁻¹·m⁻¹) at 800 °C were the lowest, which was mainly related to the formation of "glaze" layer on the coating surface at high temperature. The glaze layer consisted of two parts, which were NiCr₂O₄ oxide film with the ability of interlaminar slip formed in the outer layer and nano-grains existed in the inner layer. Worth mentioning, these nano-grains provided bearing capability while the oxide film was vital to reduce wear rate and friction coefficient. As the ambient temperature increased, many hard oxides were produced on the wear scars, including NiO, Cr₂O₃, MoO₃, and Mo₂C. They can improve tribological and mechanical properties of NiCrWMoCuCBFe coating at a wide temperature range.