We investigated the atomic configuration and the electronic structure of a BaBiO3 (BBO) thin film and its (001) surface. It was theoretically predicted that two-dimensional electron gases would be formed when the film is BiO2-terminated. We deduced depth-profile information for a BBO thin film using angle-dependent X-ray photoemission spectroscopy. Analysis of the spectral weights of the Ba 3d and Bi 4f core levels confirmed that the BBO film should have a BiO2-terminated topmost layer. We used in-situ angle-resolved photoemission spectroscopy to experimentally determine the electronic structure of a BBO thin film and found no metallic surface state. We distinguished surface states from bulk states by evaporating potassium atoms in-situ on the surface. A surface state near the bottom of the topmost bulk valence band, which was predicted by the DFT calculations, was identified. However, other surface states well separated from the bulk states were not observed. Our results provided evidence that descriptions of the BBO electronic structure require more detailed and elaborate approaches.