The results of a systematic study of photoluminescence (PL) properties of un‐doped sapphire crystals grown using different starting materials on various crystal growth methods (CZ, EFG, HDSM, Kyropoulus, HEM) are presented. Narrow line of emission has been attributed to radiation transition in Cr3+ ions (R‐line), while the nature of red wide band (RWB) of emission (600‐850 nm) is still under question. Integral intensities of R‐line and RWB were analyzed and their dependences on type of starting raw materials and of the method of crystal growth were shown. The crystals grown using Vernuil starting material exhibited significant PL in all utilized methods. On the contrary, sapphire samples grown by the same technologies wherein EMT HPDAR (High Purity Densified Alumina) was the starting material revealed much lower PL. HPDAR is produced by EMT, Inc. with proprietary and patented technology. The concentrations of various metal impurities such as Ca, Mg, Zn, Cu, Cr, Fe, Ni, H were measured. Effect of these impurities on luminescence intensity and especially the role of hydrogen incorporated into sapphire lattice are discussed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)