Photoluminescence (PL) measurements were carried out on commercial ZnO varistor samples that were electrically stressed and/or annealed at different temperatures. Changes in the intensity of green and yellow luminescence centers were studied as a function of annealing treatment. It was found that the ZnO luminescence (green and yellow) decrease with increase in annealing temperature, reach a minimum at 700°C, and increase again beyond 800°C. Furthermore, these green and yellow luminescence bands observed in the PL spectra are quenched in the ZnO varistor samples, compared to pure ZnO. In an electrically stressed ZnO varistor sample, the luminescence intensity was found to be higher compared to the as-sintered varistor sample. Annealing of the stressed varistor sample resulted in a decrease of the luminescence intensity. These PL observations are consistent with previous deep level transient spectroscopy and doppler positron annihilation spectroscopy results. All of the experimental results are consistent with the ion migration model of degradation and can be explained using a grain boundary defect model.