High-temperature photoluminescence properties of hydrothermally grown ZnO microrods were reported. Photoluminescence spectra of ZnO microrods deconvoluted into three Gaussian components: near band edge (NBE) emission, Violet emission (VL) and Yellow emission (YL) peaks corresponding to free excitons, zinc vacancies and interstitial oxygen atoms, respectively. Increasing the temperature caused a redshift of the energy position of the NBE and VL peaks and a blueshift of the energy position of the YL peak were observed. In the temperature range from 300K to 473K, the intensities of the NBE and VL bands varied based on a nonlinear pattern. Intensity of these emission bands decreases from temperature 473K–673K. As the temperature increases, changes in the energy and crystal structures of the material due to decrease in the concentration of defects cause a blueshift of the emission bands related to interstitial atoms, and a redshift of the emission bands related to vacancies.