In this work, systematic study of the thermal stability, crystal structure and electronic properties of Al doped TiO2 were studied by the first principles calculations. The results showed that Al atoms preferentially occupying the interstitial site under Ti-rich condition, but substituting the Ti atom under O-rich condition. In contrast to pure TiO2, the values of VBM and CBM are reduced for Al substituting Ti doped mode, but increased for Al interstitial atom doped mode. Thus, we can modulate the preparation condition and dosage concentration for preparing the optimal photocatalyst. (C) 2016 Elsevier B.V. All rights reserved.