This study proposes a novel sol-gel method of fabricating the two-dimensional flakes polycrystalline zinc oxide (ZnO). Apply zinc acetate dehydrate in glycerol and hydrolyzed to get the precursor zinc alkoxide particles at 160°C, and self-assemble into flakes ZnO nanostructures, and then got higer crystallinity polycrystalline ZnO after calcination for one hour at 500°C. Field-emission scanning electron microscopy (FE-SEM) was used to observe the morphology of the flakes. Its size got to a few μm2. Analyze the crystal structure and crystallinity by X-ray powder diffraction (XRD). After calcination for one hour at 500°C, we can determine it is the hexagonal wurtzite structure of ZnO. And TGA/DSC to observe the loss and phase change of the solution. The Study has successfully synthesized ZnO polycrystalline flakes by sol-gel method.