In this paper, we compare the properties of ZnO thin films on (0020020021) sapphire and GaN/c-Al 2 O 3 templates by atmospheric pressure metal–organic chemical vapor deposition (AP-MOCVD) using deionized water (H 2 O) and diethylzinc (DEZn) as the O and Zn precursors, respectively. The atomic force microscopy (AFM) images exhibited that ZnO films grown on GaN/c-Al 2 O 3 template had a regular hexagonal columnar and smooth morphology, and the ZnO grown on c-Al 2 O 3 film had the hexagonal pyramid morphology. The full widths at half maximum (FWHMs) of the (0020020022) and (10–12) ω -rocking curves of ZnO film grown on GaN/c-Al 2 O 3 template were 182 and 35802arcs, respectively, indicating the smaller mosaicity and lower dislocation density of the film compared to ZnO film grown on c-Al 2 O 3 . The room temperature PL spectra showed that the PL intensity ratio of the band-edge emission (BEE) to the deep-level emission (DLE) for the ZnO film on GaN/c-Al 2 O 3 template was larger than that of the film on c-Al 2 O 3 . Besides, the FX C (or the first excited state of A exciton) and four phonon replicas could be clearly observed in ZnO film on GaN/c-Al 2 O 3 template at 1002K compared to ZnO film on c-Al2O3 .