Surface modification is the major means to improving the wear resistance of copper alloys. In this study, Cu-Mo coatings were prepared on Cu-Cr-Zr alloy by laser cladding, and the high-temperature tribological properties against 7075 aluminum alloy were explored. The results show that the coatings are the two-phase structure of Mo encapsulated in Cu-mesh. The hardness and resistivity of the coatings is 61–73 Hb and (3.2–6.3)×10−8 Ωm, respectively. The wear resistance of the coatings is determined by hardness that relates to Mo content at lower temperatures, and it controlled by the tribo-oxides layer that composed of Cu and Mo oxides at higher temperatures. As the temperature increases, the main wear mechanism of the coatings changes from abrasive wear to adhesive wear.