The color of blue sapphire has long been explained using the intervalence charge‐transfer (IVCT) [Fe2+‐Ti4+ and/or Fe2+‐Fe3+] theory, in which the blue can be reduced by thermal (heat) treatment in oxidizing condition to alter Fe2+ (FeO) to Fe3+ (Fe2O3). However, the color mechanism is not well understood. Recently, the band gap theory proposes that iron (Fe) in sapphire always presents as Fe3+, and the blue is caused by Fe3+‐Ti4+ pair, hence thermal treatment does not alter Fe oxidation. The UV–Vis–NIR, Proton‐Induced X‐ray Emission (PIXE), and X‐ray Absorption Near‐Edge Structure (XANES) techniques are carried out before and after treatment to prove this issue. The absorption spectra are slightly lower after treatment, corresponding with the reduction of blue color in all samples. XANES data reveal mixture of Fe2+ and Fe3+ (mainly Fe3+) in all samples, and show insignificantly change after heated which rather supports the band gap theory. However, calculation based on linear combination fitting (LCF) technique shows a slight change in the oxidation from Fe2+ to Fe3+ which rather supports the IVCT theory. It is noted that the highest change is found in the lowest ratio of Fe:Ti sample, while the lowest change is conversely.