ZnO films prepared at different temperatures and annealed at 900°C in oxygen are studied by photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS). It is observed that in the PL of the as-grown films the green luminescence (GL) and the yellow luminescence (YL) are related, and after annealing the GL is restrained and the YL is enhanced. The O 1s XPS results also show the coexistence of oxygen vacancy (VO) and interstitial oxygen (Oi) before annealing and the quenching of the VO after annealing. By combining the two results it is deduced that the GL and YL are related to the VO and Oi defects, respectively.