ZnO thin films were deposited on n-Si (111) substrates at various oxygen partial pressures by pulsed laser deposition (PLD). X-ray diffraction (XRD), scanning electron microscopy (SEM) were used to analyze the influence of the oxygen partial pressure on the crystallization and morphology of the ZnO thin films. An optimal crystallized ZnO thin film was observed at the oxygen partial pressure of 6.5Pa. X-ray photoelectron spectroscopy (XPS) was used to analyze the surface components and distribution status of various elments in ZnO thin films. It was found that ZnO thin films were grown in Zn-rich state.