ZnO/Al2O3 composite coatings were fabricated by atmospheric plasma spraying technology (APS). The effects of annealing temperature and atmospheres (in air or vacuum) on the microstructure and phase transformation of the sprayed coatings were studied by scanning electron microscope (SEM) and X-ray diffraction spectroscopy (XRD). The microwave dielectric properties of these coatings after annealing treatment were also discussed in the frequency range of 8.2–12.4 GHz. Both the real part and the imaginary part of the permittivity decreased significantly with increased annealing temperature when the annealing process is carried outin air atmosphere, while the complex permittivity ofthe coating annealed in vacuum atmosphere was obviously increased compared to the initial sprayed coating. The mechanism for the variation of dielectric properties of sprayed ZnO/Al2O3 composite coating caused by annealing treatment was discussed in this study.