Zinc oxide (ZnO) thin films were deposited on GaAs (100) substrates at different temperatures in the pulsed laser deposition (PLD) system. From the measurements of X-ray diffraction (XRD) at room temperature, 300–500°C were found to be good condition for the crystallization of the thin films. From the photoluminescence (PL) measurements, 500°C was found to be the optimized temperature for its optical property. Samples grown at 100, 200, 300, and 400°C showed near band-edge (NBE) emissions and deep-level emissions. The intensity of deep-level emissions decreased as time goes on, which is believed to originate from oxygen vacancies or zinc interstitials in thin films. While for the sample grown at 500°C, bright NBE emissions were observed at room temperature, and no deep-level emissions observed. This means that the high-optical-quality thin film was grown at 500°C. At the same time, annealing process of ZnO thin films grown at room temperature was carried out in PLD chamber. It was found that the annealing temperature of 600°C has strong effects on its PL. Aging and annealing effects in ZnO thin films grown on GaAs substrates by PLD were observed for the first time.