ZnAl₂O₄ spinel powders were prepared using the Pechini or co-precipitation synthetic route and were then treated at different temperatures (600–1350 °C). These powders were characterised by X-ray diffraction, scanning electron microscopy (SEM), diffuse reflectance and luminescence measurements. SEM investigations and the X-ray patterns showed that the spinel crystallite size was dependent on the synthetic route and the treatment temperature. In addition, the structural evolution was investigated by Rietveld refinements. The inversion rate decrease was correlated with the temperature, leading to a direct spinel phase for the sample treated at high temperature. Furthermore, luminescence measurements showed various emissions linked to the presence of defects in the matrix structure. The two main emissions observed were attributed to oxygen vacancy and Zn in the interstitial positions (as revealed by differential Fourier maps). The luminescence spectra exhibited strong differences between 1200 °C and 1350 °C. At the higher temperature, the characteristic emission spectra can be attributed to the direct spinel phase. The indirect–direct spinel transformation can be monitored through the change in the optical properties and correlated to the thermal history of the sample.