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The Zn0.8Co0.2O ceramics were synthesized by the solid state reaction method with the mixture of ZnO and CoO powders. The mixed powders were sintered at 1200 °C and 1300 °C for 4 hours. It was found that the X-ray diffraction patterns of Zn0.8Co0.2O ceramics were similar to that of the pure ZnO one. The crystal structure of Zn0.8Co0.2O ceramics were then determined using the Rietveld full-profile analysis method to indicate a single phase with a wurtzite-like structure. Their microstructures were examined using the scanning electron microscopy. The results showed that their grain sizes were increased with increasing both the sintering temperatures and the doping effect. Moreover, the optical absorption spectra using UV-Vis spectrometer showed that there were several extra absorption bands appearing in the Zn0.8Co0.2O samples. This confirms that Co2+ is substituted Zn2+ in the wurtzite structure.