Influence of oxygen pressure on the epitaxy,surface morphology, and optoelectronic properties has been studied in the case of ZnOthin filmsgrown on sapphire (0001) by pulsed-laser deposition. Results of Rutherford backscattering and ion channeling in conjunction with atomic force microscopy clearly indicate that the growth mode, degree of epitaxy, and the defect density strongly depend on the oxygen background pressure during growth. It is also found that the growth mode and the defects strongly influence the electron mobility, free-electron concentration, and the luminescence properties of the ZnOfilms. By tuning the oxygen pressure during the initial and the final growth stages, smooth and epitaxialZnOfilms with high optical quality, high electron mobility, and low background carrier concentration have been obtained. The implication of these results towards the fabrication of superlattices and controlled n- and p-type doping is discussed.