In this study, the authors have investigated the structural and optical properties of ZnO layer grown by pulsed laser deposition on GaN/r-plane sapphire. X-ray diffraction results demonstrate the ZnO film to be highly preferentially deposited at a-axis orientation; the different rocking curve values along the two orthogonal directions indicate the low C 2v symmetry in the growth a-plane ZnO. From free stress to large tensile stress (about 1.34 Γ 10 9 Pa) distribution along the growth direction of ZnO is revealed by visible Raman mapping spectra. The enhanced significantly high-order longitudinal-optical (LO) phonon modes up to 4th and no TO phonons have been observed in Raman spectrum under UV 325 nm by resonance conditions; an intense and broad disorder activated surface phonon mode is also observed, resulting from the increased disorder on the film surface with stripe-like growth features. Low-temperature photoluminescence measurements reveal that the band-edge emission of ZnO is dominated by neutral donor-bound exciton and free electrons to neutral acceptor emissions. Interfacial microstructure of ZnO/GaN has been examined by transmission electron microscopy, with the epitaxial relationship (1 0 1 0) ZnO//(0 0 0 2) GaN. All these results indicated that GaN template played an important role in the growth of ZnO film, with full advantage of small lattice mismatch.