The ab initio calculation and bond valence model (BVM) are employed to investigate dopant occupancy in the Ti-doped high-temperature phase Ta2O5. In this structure, there are two types of Ta atoms, which the authors denote as Ta1 locating inside oxygen octahedral and Ta2 locating inside oxygen decahedral. The 5d state electron configuration of Ta1 and Ta2 is different, the hybridization between Ta1 5d state and O 2p state is stronger than that between Ta2 and O. The chemical bonding between Ta and oxygen ions is mainly covalent. However, there is an increase of the covalent character in going from Ta1–O bond to Ta2–O bond. Both total energy method and BVM indicate that Ti substituting Ta1 is energy favorable, and this maybe due to different electronic structures of Ta1 and Ta2.