The photoluminescence of undoped ZnO single crystals up to 1350 °C and the optical absorption of stress-relaxed, epitaxial ZnO thin films up to 1100 °C are reported. The photoluminescence intensity and power dependence with illumination flux are related to the crystal growth methods and stabilize after high temperature annealing. The observation of excitonic recombination at very high temperatures requires high illumination flux. It is found that the zero phonon line model reproduces the shift and the band gap narrowing as well as the free excitonic transition up to the cross-over with a defect level at 2.83 eV that occurs at 800 °C. A phenomenological model of the excitonic recombination band shape, taking account exciton-phonon losses and defect levels provides an excellent fit up to 2.2–2.4 eV (1100 °C). At these cross-over temperatures, an energy transfer is observed between the free exciton transition and defect transitions. However, at temperature above 1100 °C, the decrease of the band gap and the increase of thermal radiation, as well as the restrictions of our experimental set-up and particularly the illumination flux of the exciting laser, limit the analysis of the photoluminescence spectra measurements.