Two TiO2layers formed in TiAl oxidation for 50 h at 900 °C were studied using scanning transmission electron microscopy. The main efforts were placed on the investigation of the distribution of niobium. It was found that Nb enriched in TiO2grains of mixture layer but did not exist in the outer TiO2layer. High-resolution electron microscopy (HREM) Z-contrast image revealed that Nb substitute for Ti site leading to Nb enrichment in TiO2grains of the mixture layer. The formation mechanism of the two TiO2layers and the potential effect of Nb doping in the mixture layer were also discussed.