350 nm polystyrene microspheres (PSs) are prepared on sapphire substrates as masks by nanosphere lithography technique, and then ZnO thin films are grown on PS/Al₂O₃ and Al₂O₃ substrates by reactive radio frequency magnetron sputtering method, respectively. X-ray diffraction analysis, scanning electron microscope observation, and photoluminescence (PL) test are used to measure two kinds of samples after annealing; the PS mask is removed from the Al₂O₃ substrate. The results show that the grains of the ZnO thin film grown on the PS/Al₂O₃ (sample 1) are obviously worm-like; the grains of the ZnO thin film directly grown on the Al₂O₃ substrate (sample 2) show incomplete hexagonal prism shape. Although the crystallization of sample 2 is better than that of sample 1, the intensity of near band edge photoluminescence peak of sample 1 around 362 nm is 43 times stronger than that of sample 2.