Using jointly experimental results and first-principles calculations, we unambiguously assign the underlying mechanisms behind two commonly observed luminescence bands for the Al2O3 material. Indeed, we show that the red band is associated with a Ti3+ d-d transition as expected, while the blue band is the combination of the Ti3+ + O- → Ti4+ + O2- and VO•+e- → VO× de-excitation processes. Thanks to our recent developments, which take into account the vibrational contributions to the electronic transitions in solids, we were able to simulate the luminescence spectra for the different signatures. The excellent agreement with the experiment demonstrates that it should be possible to predict the color of the material with a CIE chromaticity diagram. We also anticipated the luminescence signature of Al2O3:Ti,Ca and Al2O3:Ti,Be that were confirmed by experiment.