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The Ni-base alloy composite coatings synergistically reinforced by WC and CeO2 particles were prepared on the surface of 7005 aluminum alloy by the plasma spray technique. The microstructures and the tribological properties of the composite coatings were researched. The results show that with the addition of CeO2 particles, the microstructure of the composite coating is refined; meanwhile, the WC reinforcing particles change from round to irregular polygon and their decarburization are alleviated. The friction coefficients and the wear losses of the composite coatings are lower than those of the WC/Ni-base alloy composite coatings and the Ni-base alloy coatings at different PV values. When the PV values are smaller than 3.36 N·m/s, the maximum contact stress of the composite coating is lower than its elastic limit contact stress, the wear mechanisms of which are mainly micro-cutting wear and fatigue wear. As the PV values are bigger than 3.36 N·m/s, the maximum contact stress exceeds the elastic limit contact stress of the composite coating and the contact temperature sharply increases to 648 °C, obvious plastic deformation and desquamation traces appear on the worn surface and the wear mechanisms turn into multi-plastic deformation wear, abrasive wear and adhesive wear accompanied with oxidative wear.