The influence of oxygen desorption on the photoluminescence of zinc oxide has been investigated. Photodesorption and thermal desorption of oxygen have been controlled using mass spectrometry. It has been found that the removal of oxygen from the ZnO surface leads to a manifold increase in the exciton photoluminescence intensity. The process has a reversible character. The mechanism of increase in the exciton luminescence intensity of ZnO during the oxygen desorption has been discussed.