This paper describes the observation of band bending and band edge shifts at the interfaces between nanoscale metals and TiO2 film over a wide depth range by angular-resolved hard X-ray photoemission spectroscopy (HAXPES). The HAXPES results indicate strong electrostatic interactions between the TiO2 semiconductor and metal nanoparticles, while density functional theory (DFT) calculations suggest that these interactions are primarily associated with charge transfer leading to electric dipole moments at the interface in the ground state. The effects of these dipole moments are not limited to the surface but also occur deep in the bulk of the semiconductor, and are highly dependent on the coverage of the metal nanoparticles on the semiconductor species.