ZnO films have been fabricated on (0 0 1), (0 1 1) and (1 1 1) SrTiO3 (STO) substrates by metal-organic chemical vapour deposition (MOCVD). It is interesting that the ZnO films on (0 0 1) and (0 1 1) STO substrates show polar and semipolar orientations, which are different from previous reports, while the same growing direction of polar ZnO with previous results is found on (1 1 1) STO. For the atomic arrangements, two orthogonal domains and a single domain are observed on (0 0 1) and (1 1 1) STO, respectively. Photoluminescence spectra show that every sample has a sharp near-band-edge emission peak at about 3.28 eV without any deep-level emission band between 1.5 and 2.8 eV, implying a high optical quality. A violet emission around 3.0 eV is observed only in ZnO films on (0 0 1) and (0 1 1) STO substrates grown at 600 °C, which is discussed briefly. Additionally, the semipolar ZnO does not weaken the emission efficiency along with the reduction in the polarization effect compared with polar ZnO. These results show that high-quality polar and semipolar ZnO films can be grown on STO substrates by MOCVD.