The Mo–Si–B alloys with good wear resistance are prominent for high-temperature applications. In this work, the effects of ZrB2 content and test temperature on the tribological properties of the Mo–Si–B/ZrB2 composites at 25–800 °C were investigated. It indicates that the composites show an enhanced wear resistance, which can be ascribed to the improved hardness and formation of Zr-rich borosilicate layer by introducing ZrB2 particles. The main wear mechanism is abrasive wear accompanies with adhesive wear at 25–400 °C, where ZrB2 addition can reduce the wear loss. And adhesive wear dominates at 600–800 °C, where the formed tribo-layer can provide a good self-lubricity and is beneficial for improving the wear resistance of the composites.