This paper uses a wet-chemical precipitation route to prepare radical-shaped ZnO microprisms and to deposit Cerium oxide (CeO 2 ) on the surface of ZnO, to form CeO 2 /ZnO microstructures. The samples are characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectroscopy. Their catalytic activity is also evaluated using methylene blue (MB) as a detection reagent. CeO 2 /ZnO systems exhibit higher UV absorption and transparency in the visible region. The experimental results show that the deposition of CeO 2 nanospecies is successful and that the radical-shaped microstructures of ZnO are well maintained. The CeO 2 /ZnO microstructures exhibit a much greater intensity of UV-light absorptivity and much higher photocatalytic activity than those of radical-shaped ZnO microprisms.